Reversible Protein Capture and Release by Redox-Responsive Hydrogel in Microfluidics.

Stimuli-responsive hydrogels have a wide range of potential applications in microfluidics, which has drawn great attention. Double cross-linked hydrogels are very well suited for this application as they offer both stability and the required responsive behavior. Here, we report the integration of poly(N-isopropylacrylamide) (PNiPAAm) hydrogel with a permanent cross-linker (N,N'-methylenebisacrylamide, BIS) and a redox responsive reversible cross-linker (N,N'-bis(acryloyl)cystamine, BAC) into a microfluidic device through photopolymerization. Cleavage and re-formation of disulfide bonds introduced by BAC changed the cross-linking densities of the hydrogel dots, making them swell or shrink. Rheological measurements allowed for selecting hydrogels that withstand long-term shear forces present in microfluidic devices under continuous flow. Once implemented, the thiol-disulfide exchange allowed the hydrogel dots to successfully capture and release the protein bovine serum albumin (BSA). BSA was labeled with rhodamine B and functionalized with 2-(2-pyridyldithio)-ethylamine (PDA) to introduce disulfide bonds. The reversible capture and release of the protein reached an efficiency of 83.6% in release rate and could be repeated over 3 cycles within the microfluidic device. These results demonstrate that our redox-responsive hydrogel dots enable the dynamic capture and release of various different functionalized (macro)molecules (e.g., proteins and drugs) and have a great potential to be integrated into a lab-on-a-chip device for detection and/or delivery.

Double cross-linked supramolecular hydrogels with tunable properties based on host-guest interactions.

We report a novel double cross-linked hydrogel system based on polyacrylamide and poly(2-methyl-2-oxazoline) (PMOXA) network chains, as well as on supramolecular host-guest interactions with on-demand tailored mechanical properties. Well-defined vinyl-bearing PMOXA macromonomers, functionalized with either ß-cyclodextrin units (ß-CD-PMOXA) or adamantane units (Ada-PMOXA), were synthesized and confirmed using 1H NMR, MALDI-TOF-MS and GPC measurements. The complexation between adamantane and ß-CD modified macromonomers in solution towards bismacromonomers was confirmed by 2D NOESY NMR and DLS. After introducing these bismacromonomers into the polyacrylamide hydrogel, the supramolecular non-covalent Ada/ß-CD bond was responsible for the presence of PMOXA network chains to form a dense network. Once the interactions broke, the PMOXA chains no longer contributed to the network, but became dangling graft side chains in a predominated polyacrylamide network. Their dissociative nature influenced the physical properties, including the swelling behavior and mechanics of the final hydrogel. Rheological experiments proved that the E-modulus of the network was significantly increased by the supramolecular host-guest interactions. Tuning the lengths of PMOXA network chains even allowed the modification of the changes in mechanical strength, also through the addition of free ß-CD. The tunable properties of the double cross-linked supramolecular hydrogel proved their unique strength for future applications.

"On Water" Surface-initiated Polymerization of Hydrophobic Monomers.

We present the "on water" surface-initiated Cu-mediated controlled radical polymerization ("on water" SI-CuCRP) that converts hydrophobic monomers in aqueous reaction medium to polymer brushes at unparalleled speed and efficiency. The method allows the facile conversion of a variety of common monomers under most simple reaction conditions and with minimal monomer amounts to thick and homogeneous polymer brushes. The highly living character of the "on water" SI-CuCRP allowed the preparation of decablock (homo)polymer brushes and opens the pathway to sequentially controlled polymer brushes on solids.