RESUMO
Polycyclic aromatic hydrocarbons (PAHs) are found throughout the interstellar medium and are important markers for the evolution of galaxies and both star and planet formation. They are also widely regarded as a major source of carbon, which has implications in the search for extraterrestrial life. Herein we construct a melting point phase diagram for a series of phenanthrene/pyrene binary mixtures to identify the eutectic composition (75 mol % phenanthrene) and its melting point (83 °C). The molten oil obtained on heating this eutectic composition to 90 °C in aqueous solution is homogenized in the presence of a water-soluble polymeric emulsifier. On cooling to 20 °C, polydisperse spherical phenanthrene/pyrene hybrid microparticles are obtained. Varying the stirring rate and emulsifier type enables the mean microparticle diameter to be adjusted from 11 to 279 µm. Importantly, the phenanthrene content of individual microparticles remains constant during processing, as expected for the eutectic composition. These new hybrid microparticles form impact craters and undergo partial fragmentation when fired into a metal target at 1 km s-1 using a light gas gun. When fired into an aerogel target at the same speed, microparticles are located at the ends of characteristic "carrot tracks". Autofluorescence is observed in both types of experiments, which at first sight suggests minimal degradation. However, Raman microscopy analysis of the aerogel-captured microparticles indicates prominent pyrene signals but no trace of the more volatile phenanthrene component. Such differential ablation during aerogel capture is expected to inform the in situ analysis of PAH-rich cosmic dust in future space missions.
RESUMO
Back pain is the leading cause of disability with half of cases attributed to intervertebral disc (IVD) degeneration, yet currently no therapies target this cause. We previously reported an ex vivo caprine loaded disc culture system (LDCS) that accurately represents the cellular phenotype and biomechanical environment of human IVD degeneration. Here, the efficacy of an injectable hydrogel system (LAPONITE® crosslinked pNIPAM-co-DMAc, (NPgel)) to halt or reverse the catabolic processes of IVD degeneration was investigated within the LDCS. Following enzymatic induction of degeneration using 1 mg mL-1 collagenase and 2 U mL-1 chondroitinase ABC within the LDCS for 7 days, IVDs were injected with NPgel alone or with encapsulated human bone marrow progenitor cells (BMPCs). Un-injected caprine discs served as degenerate controls. IVDs were cultured for a further 21 days within the LDCS. Tissues were then processed for histology and immunohistochemistry. No extrusion of NPgel was observed during culture. A significant decrease in histological grade of degeneration was seen in both IVDs injected with NPgel alone and NPgel seeded with BMPCs, compared to un-injected controls. Fissures within degenerate tissue were filled by NPgel and there was evidence of native cell migration into injected NPgel. The expression of healthy NP matrix markers (collagen type II and aggrecan) was increased, whereas the expression of catabolic proteins (MMP3, ADAMTS4, IL-1ß and IL-8) was decreased in NPgel (±BMPCs) injected discs, compared to degenerate controls. This demonstrates that NPgel promotes new matrix production at the same time as halting the degenerative cascade within a physiologically relevant testing platform. This highlights the potential of NPgel as a future therapy for IVD degeneration.