Liquid Crystal Elastomers—A Path to Biocompatible and Biodegradable 3D-LCE Scaffolds for Tissue Regeneration

The development of appropriate materials that can make breakthroughs in tissue engineering has long been pursued by the scientific community. Several types of material have been long tested and re-designed for this purpose. At the same time, liquid crystals (LCs) have captivated the scientific community since their discovery in 1888 and soon after were thought to be, in combination with polymers, artificial muscles. Within the past decade liquid crystal elastomers (LCE) have been attracting increasing interest for their use as smart advanced materials for biological applications. Here, we examine how LCEs can potentially be used as dynamic substrates for culturing cells, moving away from the classical two-dimensional cell-culture nature. We also briefly discuss the integration of a few technologies for the preparation of more sophisticated LCE-composite scaffolds for more dynamic biomaterials. The anisotropic properties of LCEs can be used not only to promote cell attachment and the proliferation of cells, but also to promote cell alignment under LCE-stimulated deformation. 3D LCEs are ideal materials for new insights to simulate and study the development of tissues and the complex interplay between cells

Optimizing Liquid Crystalline Elastomers for Three Dimensional Neuronal Cultures

Two dimensional (2D) tissue samples have been successfully grown using usual cell culture techniques. However, in order for cell cultures to be representative of three dimensional (3D) tissues it is necessary that they are grown in a spatial environment. Elastomers can be used for this purpose. Elastomers are a form of polymer that have elastic properties. There are multiple properties of elastomers that can be adjusted in order to provide a suitable environment for growing different cell types. The elastomer used in this project is liquid crystalline based. Its main chain is constructed of ε-caprolactam and side chains of cholesterol which gives the elastomer biocompatible properties. The use of liquid crystalline elastomers (LCE) provides a material that is anisotropic which is important for neuronal cell growth. This LCE is porous in its structure which creates a 3D matrix for cell growth making it a good candidate for supporting spatial growth of cellular structures. Elastomer pore size was measured using scanning electron microscopy (SEM) and adjusted in order to better support the growth of neuroblastoma cells. In this project human neuroblastoma cells (SHSY-5Y) were seeded within the LCE. Cells were allowed to grow for an extended period of time and imaged using confocal microscopy to better understand how the cells are growing within the LCE. The purpose of this project is to create the optimal conditions for the neuroblastoma cells by manipulating the LCE properties to control and enhance neuroblastoma cell growth.</p

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

Biphenyl-based liquid crystals for elevated temperature processing with polymers

<div><p>Due to the limited thermal stability of current commercially available liquid crystals (LCs), the incorporation into polymer composites through standard processing techniques, such as melt coextrusion, has been hindered. Motivated by this dilemma, a series of smectic B liquid crystalline structures based on the 4,4ʹ-alkyl substituted biphenyl moiety were synthesised through conventional methodologies and probed for their thermal stability and LC properties. Degradation temperatures were found to increase with increasing aliphatic chain length – up to 295 °C for C16 substituted structures, which is well above the processing temperatures of commercial polymers. Additionally, all compounds were found to be liquid crystalline in nature with crystal-to-smectic B transition temperatures ranging from 49.8 °C to 91.4 °C. Thermal stability, phase separation, and compatibility of LC/polystyrene composites were also examined. Less than 10% of 15A15 LC by weight in polystyrene exhibited good polymer miscibility, while phase separation occurred at loads higher than 15% by weight. We foresee the use of these LCs in applications that require elevated processing conditions to produce materials with enhanced mechanical or gas barrier properties.</p></div

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

Synchrotron Microbeam Diffraction Studies on the Alignment within 3D-Printed Smectic-A Liquid Crystal Elastomer Filaments during Extrusion

3D printing of novel and smart materials has received considerable attention due to its applications within biological and medical fields, mostly as they can be used to print complex architectures and particular designs. However, the internal structure during 3D printing can be problematic to resolve. We present here how time-resolved synchrotron microbeam Small-Angle X-ray Diffraction (μ-SAXD) allows us to elucidate the local orientational structure of a liquid crystal elastomer-based printed scaffold. Most reported 3D-printed liquid crystal elastomers are mainly nematic; here, we present a Smectic-A 3D-printed liquid crystal elastomer that has previously been reported to promote cell proliferation and alignment. The data obtained on the 3D-printed filaments will provide insights into the internal structure of the liquid crystal elastomer for the future fabrication of liquid crystal elastomers as responsive and anisotropic 3D cell scaffolds

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