ABSTRACT
Sulfated cellulose nanocrystals' (CNCs') facile aqueous dispersibility enables producing films, fibers, and other materials using only water as a solvent but prevents using sulfated CNCs in applications that require water immersion. We report that modifying CNCs with 3-aminopropyl-triethoxysilane (APTES) via a simple, single-pot reaction scheme dramatically improves the hydrolytic stability of CNC films. The effects of APTES modification on CNCs' properties were studied using attenuated total reflectance Fourier transform infrared spectroscopy, atomic force and optical microscopy, thermogravimetric analysis, dynamic light scattering, and ultimate analysis. Substituting a mere 12.6% of the CNCs' available hydroxyl groups with APTES dramatically increased the hydrolytic stability of shear cast films while only having minor impacts on their mechanical properties. In addition, quartz crystal microbalance with dissipation monitoring (QCMD) and multiparametric surface plasmon resonance (MP-SPR) studies showed that the CNC-APTES films also had a greater irreversible binding with carbofuran, a pesticide and emerging contaminant. These results highlight that APTES modification is a promising method for increasing the utility of sulfated CNCs in sensors, adsorbents, and other applications requiring water immersion.
ABSTRACT
Polymerized polyacrylamide (PAA) substrates are linearly elastic hydrogels that are widely used in mechanosensing studies due to their biocompatibility, wide range of functionalization capability, and tunable mechanical properties. However, such cellular response on purely elastic substrates, which do not mimic the viscoelastic living tissues, may not be physiologically relevant. Because the cellular response on 2D viscoelastic PAA substrates remains largely unknown, we used stereolithography (SLA)-based additive manufacturing technique to create viscoelastic PAA substrates with tunable mechanical properties that allow us to identify physiologically relevant cellular behaviors. Three PAA substrates of different complex moduli were fabricated by SLA. By embedding fluorescent markers during the additive manufacturing of the substrates, we show a homogeneous and uniform composition throughout, which conventional manufacturing techniques cannot produce. Rheological investigation of the additively manufactured PAA substrates shows a viscoelastic behavior with a 5-10% loss moduli compared to their elastic moduli, mimicking the living tissues. To understand the cell mechanosensing on the dissipative PAA substrates, single live cells were seeded on PAA substrates to establish the basic relationships between cell traction, cytoskeletal prestress, and cell spreading. With the increasing substrate moduli, we observed a concomitant increase in cellular traction and prestress, but not cell spreading, suggesting that cell spreading can be decoupled from traction and intracellular prestress in physiologically relevant environments. Together, additively manufactured PAA substrates fill the void of lacking real tissue like viscoelastic materials that can be used in a variety of mechanosensing studies with superior reproducibility.
ABSTRACT
A Landau-de Gennes formulation coupled with a mass-transfer equation was used to track the evaporation front and the development of chiral microstructures during the casting of sulfuric acid-hydrolyzed cellulose nanocrystal (CNC) films. These simulations are compared to thin-film casting experiments that used analogous processing parameters and environments. The results show that the initial concentration, chiral strength, surface anchoring, speed of drying, and the influence of initial shear alignment all affect the uniformity of the microstructure and the orientation of the chiral director. In this report, we aim to show that under optimal casting conditions, the lateral size of planar microstructural domains that exhibit uniform selective reflection can be achieved on the order of millimeters.
