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On the Limits of Benzophenone as Cross-Linker for Surface-Attached Polymer Hydrogels.

ABSTRACT: The synthesis of different photo-reactive poly(alkenyl norbornenes) and poly(oxonorbornenes) containing benzophenone (BP) via ring-opening metatheses polymerization (ROMP) is described. These polymers are UV irradiated to form well-defined surface-attached polymer networks and hydrogels. The relative propensity of the polymers to cross-link is evaluated by studying their gel content and its dependency on BP content, irradiation wavelength (254 or 365 nm) and energy dose applied (up to 11 J·cm^-²). Analysis of the UV spectra of the polymer networks demonstrates that the poly(oxonorbornenes) show the expected BP-induced crosslinking behavior at 365 nm, although high irradiation energy doses and BP content are needed. However, these polymers undergo chain scission at 254 nm. The poly(alkenyl norbornenes), on the other hand, do not cross-link at 365 nm, whereas moderate to good cross-linking is observed at 254 nm. UV spectra demonstrate that the cross-linking at 254 nm is due to BP cross-linking combined with a [2 + 2] cylcoaddition of the alkenyl double bonds. This indicates limitations of benzophenone as a universally applicable cross-linking for polymer networks and hydrogels.

SUBMITTER: Riga EK

PROVIDER: S-EPMC6418956 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Embedding nanomaterials into polymer hydrogels enables the design of functional materials with tailored chemical, mechanical, and optical properties. Nanocapsules that protect interior cargo and disperse readily through a polymeric matrix have drawn particular interest for their ability to integrate chemically incompatible systems and to further expand the parameter space for polymer nanocomposite hydrogels. The properties of polymer nanocomposite hydrogels depend on the material composition and processing route, which were explored systematically in this work. The gelation kinetics of network-forming polymer solutions with and without silica-coated nanocapsules bearing polyethylene glycol (PEG) surface ligands were investigated using in situ dynamic rheology measurements. Network-forming polymers comprised either 4-arm or 8-arm star PEG with terminal anthracene groups, which dimerize upon irradiation with ultraviolet (UV) light. The PEG-anthracene solutions exhibited rapid gel formation upon UV exposure (365 nm); gel formation was observed as a crossover from liquid-like to solid-like behavior during in situ small-amplitude oscillatory shear rheology. This crossover time was non-monotonic with polymer concentration. Far below the overlap concentration (c/c* ≪ 1), spatially separated PEG-anthracene molecules were subject to forming intramolecular loops over intermolecular cross-links, thereby slowing the gelation process. Near the polymer overlap concentration (c/c* ∼ 1), rapid gelation was attributed to the ideal proximity of anthracene end groups from neighboring polymer molecules. Above the overlap concentration (c/c* > 1), increased solution viscosities hindered molecular diffusion, thereby reducing the frequency of dimerization reactions. Adding nanocapsules to PEG-anthracene solutions resulted in faster gelation than nanocapsule-free PEG-anthracene solutions with equivalent effective polymer concentrations. The final elastic modulus of nanocomposite hydrogels increased with nanocapsule volume fraction, signifying synergistic mechanical reinforcement by nanocapsules despite not being cross-linked into the polymer network. Overall, these findings quantify the impact of nanocapsule addition on the gelation kinetics and mechanical properties of polymer nanocomposite hydrogels, which are promising materials for applications in optoelectronics, biotechnology, and additive manufacturing.

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On the Limits of Benzophenone as Cross-Linker for Surface-Attached Polymer Hydrogels.

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