Self-assembly of single amino acid/pyrene conjugates with unique structure-morphology relationship.

This article describes the self-assembly of π-conjugated building blocks composed of single amino acid and pyrene (Py) moieties. In aqueous conditions, the Py-capped amino acids undergo self-assembly through various non-covalent interactions such as hydrogen-bonding, π-π stacking as well as electrostatic interactions to form supramolecular nanostructures in acidic and basic conditions. Interestingly, we found that the blend of different Py-gelators with oppositely charged amino acids (Py-Glu and Py-Lys) displays unique nano-structural morphologies and gelation properties of the resulting hydrogels at physiological pH when compared with single Py conjugates, which was attributed to additional electrostatic interactions. Overall, this report illustrates the importance of two-component supramolecular co-assembled hydrogels and their structure-morphology relationship, improved mechanical properties, and biocompatibility and thus provides a new insight into the design of self-assembled nanomaterials.

Glucosamine-Based Supramolecular Nanotubes for Human Mesenchymal Cell Therapy.

Herein, we demonstrate an example of glucosamine-based supramolecular hydrogels that can be used for human mesenchymal cell therapy. We designed and synthesized a series of amino acid derivatives based on a strategy of capping d-glucosamine moiety at the C-terminus and fluorinated benzyl group at the N-terminus. From a systematic study on chemical structures, we discovered that the glucosamine-based supramolecular hydrogel [pentafluorobenzyl (PFB)-F-Glu] self-assembled with one-dimensional nanotubular structures at physiological pH. The self-assembly of a newly discovered PFB-F-Glu motif is attributed to the synergistic effect of π-π stacking and extensive intermolecular hydrogen bonding network in aqueous medium. Notably, PFB-F-Glu nanotubes are proven to be nontoxic to human mesenchymal stem cells (hMSCs) and have been shown to enhance hMSC proliferation while maintaining their pluripotency. Retaining of pluripotency capabilities provides potentially unlimited source of undifferentiated cells for the treatment of future cell therapies. Furthermore, hMSCs cultured on PFB-F-Glu are able to secrete paracrine factors that downregulate profibrotic gene expression in lipopolysaccharide-treated human skin fibroblasts, which demonstrates that PFB-F-Glu nanotubes have the potential to be used for wound healing applications. Overall, this article addresses the importance of chemical design to generate supramolecular biomaterials for stem cell therapy.

The formulation and characterization of 3D printed grafts as vascular access for potential use in hemodialysis.

Arteriovenous graft (AVG) failure continues to be a life-threatening problem in haemodialysis. Graft failure can occur if the implanted graft is not well-matched to the vasculature of the patient. Likewise, stenosis often develops at the vein-graft anastomosis, contributing to thrombosis and early graft failure. To address this clinical need, a novel ink formulation comprised of ACMO/TMPTA/TMETA for 3D printing a AVG was developed (ACMO-AVG), in which the printed AVG was biocompatible and did not induce cytotoxicity. The ease of customizing the ACMO-AVG according to different requirements was demonstrated. Furthermore, the AVG displayed similar mechanical properties to the commercially available arteriovenous ePTFE graft (ePTFE-AVG). Unlike ePTFE-AVG, the ACMO-AVG displayed excellent anti-fouling characteristics because no plasma protein adsorption and platelet adhesion were detected on the luminal surfaces after 2 h of incubation. Similarly, exposure to human endothelial cells and human vascular smooth muscle cells did not result in any cell detection on the surfaces of the ACMO-AVG. Thus, the present study demonstrates a newly developed 3D printing ink formulation that can be successfully 3D printed into a clinically applicable vascular access used for haemodialysis.