Synthesis, Characterization, and Digital Light Processing of a Hydrolytically Degradable Hyaluronic Acid Hydrogel.

Numerous chemical modifications of hyaluronic acid (HA) have been explored for the formation of degradable hydrogels that are suitable for a variety of biomedical applications, including biofabrication and drug delivery. Thiol-ene step-growth chemistry is of particular interest due to its lower oxygen sensitivity and ability to precisely tune mechanical properties. Here, we utilize an aqueous esterification route via reaction with carbic anhydride to synthesize norbornene-modified HA (NorHACA) that is amenable to thiol-ene crosslinking to form hydrolytically unstable networks. NorHACA is first synthesized with varying degrees of modification (∼15-100%) by adjusting the ratio of reactive carbic anhydride to HA. Thereafter, NorHACA is reacted with dithiol crosslinker in the presence of visible light and photoinitiator to form hydrogels within tens of seconds. Unlike conventional NorHA, NorHACA hydrogels are highly susceptible to hydrolytic degradation through enhanced ester hydrolysis. Both the mechanical properties and the degradation timescales of NorHACA hydrogels are tuned via macromer concentration and/or the degree of modification. Moreover, the degradation behavior of NorHACA hydrogels is validated through a statistical-co-kinetic model of ester hydrolysis. The rapid degradation of NorHACA hydrogels can be adjusted by incorporating small amounts of slowly degrading NorHA macromer into the network. Further, NorHACA hydrogels are implemented as digital light processing (DLP) resins to fabricate hydrolytically degradable scaffolds with complex, macroporous structures that can incorporate cell-adhesive sites for cell attachment and proliferation after fabrication. Additionally, DLP bioprinting of NorHACA hydrogels to form cell-laden constructs with high viability is demonstrated, making them useful for applications in tissue engineering and regenerative medicine.

Ontogenetic variation in the sensory structures on the pedipalps of cosmetid harvestmen (Arachnida, Opiliones, Laniatores).

In arachnids, pedipalps are highly variable appendages that may be used in feeding, courtship, defense, and agonistic encounters. In cosmetid harvestmen, adults have pedipalps that feature flattened femora, spoon-shaped tibiae, and robust tarsal claws. In contrast, the pedipalps of nymphs are elongate with cylindrical podomeres and are adorned with delicate pretarsi. In this study, we used scanning electron microscopy to examine the distribution of cuticular structures (e.g., sensilla chaetica, pores) on the elements of the pedipalps of adults and nymphs of three species of cosmetid harvestmen. Our results indicate that there is considerable ontogenetic variation in the morphology of the trochanter, femur, patella, tibia, and tarsus. The pretarsus of the nymph has a ventral patch of setae that is absent from the adult tarsal claw. We observed this structure on all three cosmetid species as well as on the pedipalps of an additional seven morphospecies of nymphs collected in Belize and Costa Rica. This structure may represent a previously unrecognized autapomorphy for Cosmetidae. Examinations of the pedipalps of antepenultimate nymphs of additional gonyleptoidean harvestmen representing the families Ampycidae, Cranaidae, Manaosbiidae, and Stygnidae revealed the occurrence of unusual, plumose tarsal setae, but no setal patches on the tarsal claw.