One-shot Synthesis of Star Gradient Copolymers with Controllable Graft Density

Long-standing conventional synthetic methods limit the scope of polymer architectural design such as connectivity, sequence and symmetry. Herein, we report a series of star gradient copolymers with variable grafting densities...

Theoretical and Experimental Optimization of the Graft Density of Functionalized Anti-Biofouling Surfaces by Cationic Brushes

Diseases and complications related to catheter materials are severe problems in biomedical material applications, increasing the infection risk and medical expenses. Therefore, there is an enormous demand for catheter materials with antibacterial and antifouling properties. Considering this, in this work, we developed an approach of constructing antibacterial surfaces on polyurethane (PU) via surface-initiated atom transfer radical polymerization (SI-ATRP). A variety of cationic polymers were grafted on PU. The biocompatibility and antifouling properties of all resulting materials were evaluated and compared. We also used a theoretical algorithm to investigate the anticoagulant mechanism of our PU-based grafts. The hemocompatibility and anti-biofouling performance improved at a 86–112 μg/cm2 grafting density. The theoretical simulation demonstrated that the in vivo anti-fouling performance and optimal biocompatibility of our PU-based materials could be achieved at a 20% grafting degree. We also discuss the mechanism responsible for the hemocompatibility of the cationic brushes fabricated in this work. The results reported in this paper provide insights and novel ideas on material design for applications related to medical catheters.

Improvement of PLLA Ductility by Blending with PVDF: Localization of Compatibilizers at Interface and Its Glycidyl Methacrylate Content Dependency

In this work, the localization of reactive compatibilizer (RC, containing poly(methyl methacrylate) (PMMA) backbone with randomly distributed glycidyl methacrylate (GMA) on it) at the polyvinylidene fluoride/poly(l-lactic acid) (PVDF/PLLA) interface has been manipulated by means of GMA contents. At the very beginning of mixing, RC tends to stay in the PVDF phase due to the miscibility between PVDF and PMMA. Upon further shearing, more and more PLLA chains have been grafted on PMMA backbone, producing PLLA–g–PMMA copolymer. The balanced stress on two sides accounts for the localization of compatibilizers at the PVDF/PLLA interface. Finally, the stress of the PLLA side has been enhanced remarkably due to the higher graft density of PLLA, resulting in the enrichment of the copolymer in the PLLA matrix. The migration of RC from the PVDF phase to the immiscible interface and PLLA matrix can be accelerated by employing RC with higher GMA content. Furthermore, the compatibilizer localization produces a significant influence on the morphology and ductility of the PVDF/PLLA blend. Only when the compatibilizers precisely localize at the interface, the blend exhibits the smallest domain and highest elongation at break. Our results are of great significance for not only the fabrication of PLLA with high ductility, but also the precise localization of compatibilizers at the interface of the immiscible blend.

Precise polyethylene derivatives bearing mesogenic side-chains: delicate self-assembly depending on graft density

Precise polyethylene derivatives bearing mesogenic side-chains demonstrate a sophisticated side-chain spacing effect on the local coupling and spatial arrangement of the backbone and side-chains.