Controlling Anti-Penetration Performance by Post-Grafting of Fluorinated Alkyl Chains onto Polystyrene-block-poly(vinyl methyl siloxane).

Polydimethylsiloxane (PDMS) has been widely used as a surface coating material, which has been reported to possess dynamic omniphobicity to a wide range of both polar and nonpolar solvents due to its high segmental flexibility and mobility. However, such high flexibility and mobility also enable penetration of small molecules into PDMS coatings, which alter the chemical and physical properties of the coating layers. To improve the anti-penetration properties of PDMS, a series of fluorinated alkyl segments are grafted to a diblock copolymer of polystyrene-block-poly(vinyl methyl siloxane) (PS-b-PVMS) using thiol-ene click reactions. This article reports the chemical characterization of these model fluorosilicone block copolymers and uses fluorescence measurements to investigate the dye penetration characteristics of polymer thin films. The introduction of longer fluorinated alkyl chains can gradually increase the anti-penetration properties as the time to reach the maximum fluorescence intensity (tpeak) gradually increases from 11 s of PS-b-PVMS to more than 1000 s of PS-b-P(n-C6F13-VMS). The improvement of anti-penetration properties is attributed to stronger inter-/intrachain interactions, phase segregation of ordered fluorinated side chains, and enhanced hydrophobicity caused by the grafting of fluorinated alkyl chains.

Visualizing Penetration of Fluorescent Dye through Polymer Coatings.

Understanding how small molecules penetrate and contaminate polymer films is of vital importance for developing protective coatings for a wide range of applications. To this end, rhodamine B fluorescent dye is visualized diffusing through polystyrene-polydimethylsiloxane block copolymer (BCP) coatings using confocal microscopy. The intensity of dye inside the coatings grows and decays non-monotonically, which is likely due to a combination of dye molecule transport occurring concurrently in different directions. An empirical fitting equation allows for comparing the contamination rates between copolymers, demonstrating that dye penetration is related to the chemical makeup and configuration of the BCPs. This work shows that confocal microscopy can be a useful tool to visualize the transport of a fluorophore in space and time through a coating.

Capillary detachment of a microparticle from a liquid-liquid interface.

The attachment and detachment of microparticles at a liquid-liquid interface are common in many material systems, from Pickering emulsions and colloidal assemblies to capillary suspensions. Properties of these systems rely on how the particles interact with the liquid-liquid interface, including the detachment process. In this study, we simultaneously measure the capillary detachment force of a microparticle from a liquid-liquid interface and visualize the shape of the meniscus by combining colloidal probe microscopy and confocal microscopy. The capillary behavior is studied on both untreated (hydrophilic) and fluorinated (hydrophobic) glass microparticles. The measured force data show good agreement with theoretical calculations based on the extracted geometric parameters from confocal images of the capillary bridge. It is also evident that contact line pinning is an important aspect of detachment for both untreated and fluorinated particles.

Temperature-dependent soft wetting on amorphous, uncrosslinked polymer surfaces.

The wetting of polymer melts at high temperatures is studied by placing a glycerol drop on a poly(n-butyl methacrylate) film and measuring the wetting ridge. The height of the wetting ridge grows continuously over time. These wetting ridge growth rates can be explained by polymer chain dynamics occurring at the molecular level, determined using oscillatory shear rheology of the polymer melt. The shape of wetting ridge profile can be modeled using an equation previously used for elastomers, with a simple modification that incorporates the time-dependent storage modulus of the uncrosslinked melts.

Erodible thermogelling hydrogels for localized mitochondrial transplantation to the spinal cord.

We developed a thermal-gelling, erodible hydrogel system for localized delivery of viable mitochondria in vivo, as well as labeled transplanted mitochondria with specific dyes and/or genetically modified mitochondria tagged with red fluorescence protein (RFP). We also employed cell lines to optimize a hydrogel composed of methylcellulose and hyaluronic acid designed to preserve bioenergetics while facilitating mitochondrial release. We further investigated how transplantation of allogeneic or xenogeneic mitochondria into respective cell lines affects host cellular metabolism, as measured by MTS assay. We found that 70% of mitochondria are released from the hydrogel within 20 min at 37 °C, that the respiratory capacity of hydrogel-released mitochondria over 60 min was greater than those without gel, and that MTR-labeling of mitochondria is not indelible. RFP-tagged transgenic mitochondria isolated from modified SH-SY5Y human neuroblastoma cells showed effective uptake into both naïve SH-SY5Y cells and rat PC-12 cells, notably when released from hydrogel. The hydrogel both protected the mitochondria at physiological conditions in vitro while solidifying and diffusing within 60 min locally in situ. To assess metabolic effects, both cell lines were transplanted with different concentrations of SH-SY5Y or PC-12 cell line-derived mitochondria and all resulted in significant increases in metabolism at 6- and 24-hour after transplantation. Alternatively, transplanted mitochondria at highest concentration from rat brain and spinal cord tissues reduced metabolic activities after 24-hour. Along with hydrogel refinements, we are further investigating whether such metabolic changes are due to alterations in cell proliferation or the number of exogenous mitochondria incorporated into individual host cells.