A Molecular Rheology Dynamics Study on 3D Printing of Liquid Crystal Elastomers.

This work presents a rheological study of a biocompatible and biodegradable liquid crystal elastomer (LCE) ink for three dimensional (3D) printing. These materials have shown that their structural variations have an effect on morphology, mechanical properties, alignment, and their impact on cell response. Within the last decade LCEs are extensively studied as potential printing materials for soft robotics applications, due to the actuation properties that are produced when liquid crystal (LC) moieties are induced through external stimuli.

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 (,)-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.

Physical Models from Physical Templates Using Biocompatible Liquid Crystal Elastomers as Morphologically Programmable Inks For 3D Printing.

Advanced manufacturing has received considerable attention as a tool for the fabrication of cell scaffolds however, finding ideal biocompatible and biodegradable materials that fit the correct parameters for 3D printing and guide cells to align remain a challenge. Herein, a photocrosslinkable smectic-A (Sm-A) liquid crystal elastomer (LCE) designed for 3D printing is presented, that promotes cell proliferation but most importantly induces cell anisotropy. The LCE-based bio-ink allows the 3D duplication of a highly complex brain structure generated from an animal model.

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 (||). 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.

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).

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.

3D Porous Liquid Crystal Elastomer Foams Supporting Long-term Neuronal Cultures.

3D liquid crystal elastomer (3D-LCE) foams are used to support long-term neuronal cultures for over 60 days. Sequential imaging shows that cell density remains relatively constant throughout the culture period while the number of cells per observational area increases. In a subset of samples, retinoic acid is used to stimulate extensive neuritic outgrowth and maturation of proliferated neurons within the LCEs, inducing a threefold increase in length with cells displaying morphologies indicative of mature neurons.

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.

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.

Synthesis of Biocompatible Liquid Crystal Elastomer Foams as Cell Scaffolds for 3D Spatial Cell Cultures.

Here, we present a step-by-step preparation of a 3D, biodegradable, foam-like cell scaffold. These scaffolds were prepared by cross-linking star block co-polymers featuring cholesterol units as side-chain pendant groups, resulting in smectic-A (SmA) liquid crystal elastomers (LCEs). Foam-like scaffolds, prepared using metal templates, feature interconnected microchannels, making them suitable as 3D cell culture scaffolds.