RESUMEN
Hydrogel microparticles (HMPs) have been investigated widely for their use in tissue engineering and drug delivery applications. However, translation of these highly tunable systems has been hindered by covalent cross-linking methods within microparticles. Stereocomplexation, a stereospecific form of physical cross-linking, provides a robust yet degradable alternative for creating translationally relevant HMPs. Herein, 4-arm polyethylene glycol (PEG) stars were used as macromolecular initiators from which oligomeric poly(l-lactic acid) (PLLA) was polymerized with a degree of polymerization (DPn) of 20 on each arm. Similarly, complementary propargyl-containing ABA cross-linkers with enantiomeric poly(d-lactic acid) (PDLA) segments (DPn = 20) on each arm. Droplets of these gel precursors were formed via a microfluidic organic-in-oil-in-water system where microparticles self-assembled via stereocomplexation and were stabilized after precipitation in deionized water. By varying the flow rate of the dispersed phase, well-defined microparticles with diameters of 33.7 ± 0.5, 62.4 ± 0.6, and 105.7 ± 0.8 µm were fabricated. Gelation due to stereocomplexation was confirmed via wide-angle X-ray scattering in which HMPs exhibited the signature diffraction pattern of stereocomplexed PLA at 2θ = 12.2, 21.2, 24.2°. Differential scanning calorimetry also confirmed stereocomplexation by the appearance of a crystallization exotherm (Tc = 37 °C) and a high-temperature endotherm (Tm = 159 °C) that does not appear in the homocrystallization of PLLA or the hydrogel precursors. Additionally, the propargyl handle present on the cross-linker allows for pre- or post-assembly thiol-yne "click" functionalization as demonstrated by the addition of thiol-containing fluorophores to the HMPs.
RESUMEN
Printed carbon nanotube thin-film transistors (CNT-TFTs) are candidates for flexible electronics with printability on a wide range of substrates. Among the layers comprising a CNT-TFT, the gate dielectric has proven most difficult to additively print owing to challenges in film uniformity, thickness, and post-processing requirements. Printed ionic dielectrics show promise for addressing these issues and yielding devices that operate at low voltages thanks to their high-capacitance electric double layers. However, the printing of ionic dielectrics in their various compositions is not well understood, nor is the impact of certain stresses on these materials. In this work, we studied three compositionally distinct ionic dielectrics in fully printed CNT-TFTs: the polar-fluorinated polymer elastomer PVDF-HFP; an ion gel consisting of triblock polymer PS-PMMA-PS and ionic liquid EMIM-TFSI; and crystalline nanocellulose (CNC) with a salt concentration of 0.05%. Although ion gel has been thoroughly studied, e-PVDF-HFP and CNC printing are relatively new and this study provides insights into their ink formulation, print processing, and performance as gate dielectrics. Using a consistent aerosol jet printing approach, each ionic dielectric was printed into similar CNT-TFTs, allowing for direct comparison through extensive characterization, including mechanical and electrical stress tests. The ionic dielectrics were found to have distinct operational dependencies based on their compositional and ionic attributes. Overall, the results reveal a number of trade-offs that must be managed when selecting a printable ionic dielectric, with CNC showing the strongest performance for low-voltage operation but the ion gel and elastomer exhibiting better stability under bias and mechanical stresses.
