Chemical-PDMS binding kinetics and implications for bioavailability in microfluidic devices

Microfluidic organ-on-chip devices constructed from polydimethylsiloxane (PDMS) have proven useful in studying both beneficial and adverse effects of drugs, supplements, and potential toxicants. Despite multiple advantages, one clear drawback of PDMS-based devices is binding of hydrophobic chemicals to their exposed surfaces. Chemical binding to PDMS can change the timing and extent of chemical delivery to cells in such devices, potentially altering dose-response curves. Recent efforts have quantified PDMS binding for selected chemicals. Here, we test a wider set of nineteen chemicals using UV-vis or infrared spectroscopy to characterize loss of chemical from solution in two setups with different PDMS-surface-to-solution-volume ratios. We find discernible PDMS binding for eight chemicals and show that PDMS binding is strongest for chemicals with a high octanol-water partition coefficient (log P > 1.85) and low H-bond donor number. Further, by measuring depletion and return of chemical from solution over tens to hundreds of hours and fitting these results to a first order model of binding kinetics, we characterize partitioning into PDMS in terms of binding capacities per unit surface area and both forward and reverse rate constants. These fitted parameters were used to model the impact of PDMS binding on chemical transport and bioavailability under realistic flow conditions and device geometry. The models predict that PDMS binding could alter in-device cellular exposures for both continuous and bolus dosing schemes by up to an order of magnitude compared to nominal input doses. We measure chemical-PDMS binding for 19 chemicals, correlate binding with molecular properties, and use measured kinetics to model in-device bioavailability.