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. This report utilizes experiments and coarse-grained molecular dynamics to study the macroscopic rheology of LCEs in nonlinear shear flow. Results from the shear flow simulations are in line with the outcomes of these experimental investigations. This work believes the insights from these results can be used to design and print new material with desirable properties necessary for targeted applications.

An Ex Vivo Porcine Model for Hydrodynamic Testing of Experimental Aortic Valve Procedures and Novel Medical Devices.

The options for testing new cardiac procedures and investigative medical devices prior to use in an animal model are limited. In this study, we present a method for mounting a porcine aortic valve in a pulse duplicator to evaluate its hydrodynamic properties. These properties can then be evaluated before and after the procedure under investigation is performed and/or the investigative medical device is applied. Securing the inflow segment presents some difficulty owing to the lack of circumferential myocardium in the left ventricular outflow tract. This method addresses that issue by securing the inflow segment using the anterior leaflet of the mitral valve and then suturing the left ventricular free wall around the inflow fixture. The outflow segment is secured simply by inserting the fixture into an incision in the superior aspect of the aortic arch. We found that specimens had significantly different hydrodynamic properties before and after tissue fixation. This finding induced us to use fresh specimens in our testing and should be considered when using this method. In our work, we used this method to test novel intracardiac patch materials for use in the valvular position by performing an aortic valve neocuspidization procedure (Ozaki procedure) on the mounted porcine aortic valves. These valves were tested before and after the procedure to assess the change in hydrodynamic properties in comparison to the native valve. Herein, we report a platform for hydrodynamic testing of experimental aortic valve procedures that enables comparison with the native valve and between different devices and techniques used for the procedure under investigation.

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. Vascular tissue models are generated from fluorescently stained mouse tissue spatially imaged using confocal microscopy and subsequently processed to create a digital 3D model suitable for printing. The 3D structure is reproduced using a Digital Light Processing (DLP) stereolithography (SLA) desktop 3D printer. Synchrotron Small-Angle X-ray Diffraction (SAXD) data reveal a strong alignment of the LCE layering within the struts of the printed 3D scaffold. The resultant anisotropy of the LCE struts is then shown to direct cell growth. This study offers a simple approach to produce model tissues built within hours that promote cellular alignment.

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. Designed LCEs' micro-channels have a similar diameter to endogenous parenchymal arterioles, ensuring that neurons throughout the construct have constant access to growth media during extended experiments. Here it is shown that 3D-LCEs provide a unique environment and simple method to longitudinally study spatial neuronal function, not possible in conventional culture environments, with simplistic integration into existing methodological pipelines.

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.

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. The combined properties of the regular structure of the metal foam and of the elastomer result in a 3D cell scaffold that promotes not only higher cell proliferation compared to conventional porous templated films, but also better management of mass transport (i.e., nutrients, gases, waste, etc.). The nature of the metal template allows for the easy manipulation of foam shapes (i.e., rolls or films) and for the preparation of scaffolds of different pore sizes for different cell studies while preserving the interconnected porous nature of the template. The etching process does not affect the chemistry of the elastomers, preserving their biocompatible and biodegradable nature. We show that these smectic LCEs, when grown for extensive time periods, enable the study of clinically relevant and complex tissue constructs while promoting the growth and proliferation of cells.

Test of Halperin-Lubensky-Ma crossover function at the N-Sm-A transition in liquid crystal binary mixtures via high-resolution birefringence measurements.

We report optical birefringence data for a series of mixtures of the liquid crystals octylcyanobiphenyl (8CB) and decylcyanobiphenyl (10CB). Nematic order parameter S data in the nematic and smectic A phases have been derived from phase angle changes obtained in temperature scans with a rotating analyzer method. These S values have been used to arrive at values for possible entropy discontinuities at the smectic A to nematic phase transition temperature T_{NA}. The 10CB mole fraction dependence of the obtained entropy discontinuities could be well fitted with a crossover function consistent with the mean-field free-energy expression with a nonzero cubic term arising from the coupling between the smectic-A order parameter and the orientational order parameter director fluctuations in the Halperin-Lubensky-Ma theory. The obtained results are in good agreement with existing results from adiabatic scanning calorimetry. By exploiting the fact that the temperature derivative of the order parameter S(T) near T_{NA} exhibits the same power law divergence as the specific heat capacity, we have extracted the effective critical exponent α values for the compositions under study. The critical exponent α has been observed to reach the tricritical value α_{TCP}=0.5 for the 10CB mole fraction of x=0.330.