Biodegradable Poly(l-lactic acid) (PLLA) Coatings Fabricated from Nonsolvent Induced Phase Separation for Improving Corrosion Resistance of Magnesium Rods in Biological Fluids.

Magnesium (Mg)-based biometals are increasingly becoming a promising candidate of the next-generation implantable materials due to their unique properties, such as high biocompatibility, favorable mechanical strength, and good biodegradability in physiological conditions. However, the swift corrosion of Mg, resulting in early loss of structural support, has posed an enormous challenge in clinical application of Mg-based implants. To overcome these limitations, herein we developed a novel method, which combines the traditional dip-coating with nonsolvent induced phase separation (NIPS), to fabricate biodegradable PLLA coatings with controlled membrane morphology on pure Mg rods. Unlike the conventional dip-coating, where the polymer solution on the Mg substrates is left to evaporate directly under proper atmosphere, in NIPS, the polymer solution on the substrates is not left to dry but immersed in a nonsolvent of the PLLA, leading to the precipitation of polymer networks. Our results demonstrated that various polymer coatings with different morphologies and inner structures could be easily fabricated by a careful selection of nonsolvents. In comparison to dense PLLA coatings obtained from conventional solvent evaporation, PLLA coatings with a dense surface and porous inner structure were obtained when hexane and petroleum ether were used as the nonsolvents, while PLLA coatings with a completely porous structure were obtained when polar acetone and ethanol were chosen. The electrochemical corrosion tests and immersion tests further showed that all polymer coatings could significantly improve the corrosion resistance and suppress the corrosion rates of the substrates. However, PLLA films obtained via NIPS had much lower pH changes and slower Mg2+ release, implying better protective effects of the fabricated coatings. Based on results of all experiments, a new process for the corrosion mechanism of Mg implants during immersion has also been proposed in this work.

Dopamine Polymerization in Liquid Marbles: A General Route to Janus Particle Synthesis.

Coating a liquid with a particle shell not only renders a droplet superhydrophobic but also isolates a well-confined microenvironment for miniaturized chemical processes. Previously, we have demonstrated that particles at the liquid marble interface provide an ideal platform for the site-selective modification of superhydrophobic particles. However, the need for a special chemical reaction limits their potential use for the fabrication of Janus particles with various properties. Herein, we combine the employment of liquid marbles as microreactors with the remarkable adhesive ability of polydopamine to develop a general route for the synthesis of Janus particles from micrometer-sized superhydrophobic particles. We demonstrate that dopamine polymerization and deposition inside liquid marbles could be used for the selective surface modification of microsized silica particles, resulting in the formation of Janus particles. Moreover, it is possible to manipulate the Janus balance of the particles via the addition of surfactants and/or organic solvents to tune the interfacial energy. More importantly, owing to the many functional groups in polydopamine, we show that versatile strategies could be introduced to use these partially polydopamine-coated silica particles as platforms for further modification, including nanoparticle immobilization, metal ion chelation and reduction, as well as for chemical reactions. Given the flexibility in the choice of cores and the modification strategies, this developed method is distinctive in its high universality, good controllability, and great practicability.

Liquid marbles stabilized by charged polymer latexes: how does the drying of the latex particles affect the properties of liquid marbles?

The coating of solid particles on the surface of liquid in air makes liquid marbles a promising approach in the transportation of a small amount of liquid. The stabilization of liquid marbles by polymeric latex particles imparts extra triggers such as pH and temperature, leading to the remote manipulation of droplets for many potential applications. Because the functionalized polymeric latexes can exist either as colloidally stable latex or as flocculated latex in a dispersion, the drying of latex dispersions under different conditions may play a significant role in the stabilization of subsequent liquid marbles. This article presents the investigation of liquid marbles stabilized by poly(styrene-co-methacrylic acid) (PS-co-MAA) particles drying under varied conditions. Protonation of the particles before freeze drying makes the particles excellent liquid marble stabilizers, but it is hard to stabilize liquid marbles for particles dried in their deprotonated states. The static properties of liquid marbles with increasing concentrations of protonating reagent revealed that the liquid marbles are gradually undermined by protonating the stabilizers. Furthermore, the liquid marbles stabilized by different particles showed distinct behaviors in separation and merging manipulated by tweezers. This study shows that the initial state of the particles should be carefully taken into account in formulating liquid marbles.

Injectable magnesium oxychloride cement foam-derived scaffold for augmenting osteoporotic defect repair.

HYPOTHESIS: Cement augmentation has been widely applied to promote osteoporotic fracture healing, whereas the existing calcium-based products suffer from the excessively slow degradation, which may impede bone regeneration. Magnesium oxychloride cement (MOC) shows promising biodegradation tendency and bioactivity, which is expected to be a potential alternative to the classic calcium-based cement for hard-tissue-engineering applications. EXPERIMENTS: Here, a hierarchical porous MOC foam (MOCF)-derived scaffold with favorable bio-resorption kinetic and superior bioactivity is fabricated through Pickering foaming technique. Then, a systematic characterization in terms of material properties and in vitro biological performance have been conducted to evaluate the feasibility of the as-prepared MOCF scaffold to be a bone-augmenting material for treating osteoporotic defects. FINDINGS: The developed MOCF shows excellent handling performance in the paste state, while exhibiting sufficient load-bearing capacity after solidification. In comparison with the traditional bone cement, calcium deficient hydroxyapatite (CDHA), our porous MOCF scaffold demonstrates a much higher biodegradation tendency and better cell recruitment ability. Additionally, the eluted bioactive ions by MOCF commits to a biologically inductive microenvironment, where the in vitro osteogenesis is significantly enhanced. It is anticipated that this advanced MOCF scaffold will be competitive for clinical therapies to augment osteoporotic bone regeneration.

Development of a novel biodegradable and anti-bacterial polyurethane coating for biomedical magnesium rods.

Surface modification of biomedical Mg with functional polymers coatings is an effective and simple strategy to improve the corrosion resistance and anti-bacterial property. Herein, we develop a novel biodegradable and anti-bacterial polymer coating for Mg rods. A key feature of our approach is to treat the Mg rods with polyurethane, a widely used coating material with strong structural controllability and good film-formation property. Polyurethanes (PU) functionalized by polyethylene glycol (PEG) chains (GPU) and zwitterions (ZPU) were firstly synthesized and subsequently applied to fabricate coatings on Mg-based rods. Scanning electron microscopy (SEM) result demonstrates that a homogeneous and dense layer with a thickness of ~4-15 µm is readily formed on the substrates by dip-coating method. We first investigated how PU coatings would affect their resulting corrosion behaviors by the electrochemical corrosion test, surface morphology examining and element analysis of the immersed samples. Then, we evaluated their protection capabilities and the relationship to Mg2+ ion release and pH value alteration under the physiological conditions. Results show that the corrosion resistance of Mg rods is improved appreciably after coating with the synthesized PU polymers. More importantly, the functionalized PU exhibit enhanced antibacterial performance and excellent blood compatibility. In particular, ZPU-12 not only successfully improves the corrosion resistance of substrates, but also produces an antimicrobial coating for preventing bacterial attachment. The application of these functionalized PU coatings for the surface modification of biomedical Mg-based alloys can provide a practical and potential strategy to expedite their clinical acceptance.