Photoactivated Cyclic Polyphthalaldehyde Microcapsules for Payload Delivery.

Microcapsules with a cyclic polyphthalaldehyde (cPPA) shell and oil core were fabricated by an emulsification process. The low ceiling temperature cPPA shell was made phototriggerable by incorporating a photoacid generator (PAG). Photoactivation of the PAG created a strong acid which catalyzed cPPA depolymerization, resulting in the release of the core payload, as quantified by 1H NMR. The high molecular weight cPPA (197 kDa) yielded uniform spherical microcapsules. The core diameter was 24.8 times greater than the cPPA shell thickness (2.4 to 21.6 µm). Nonionic bis(cyclohexylsulfonyl)diazomethane (BCSD) and N-hydroxynaphthalimide triflate (HNT) PAGs were used as the PAG in the microcapsule shells. BCSD required dual stimuli of UV radiation and post-exposure baking at 60 °C to activate cPPA depolymerization while room temperature irradiation of HNT resulted in instantaneous core release. A 300 s UV exposure (365 nm, 10.8 J/cm2) of the cPPA/HNT microcapsules resulted in 66.5 ± 9.4% core release. Faster core release was achieved by replacing cPPA with a phthalaldehyde/propanal copolymer. A 30 s UV exposure (365 nm, 1.08 J/cm2) resulted in 82 ± 13% core release for the 75 mol % phthalaldehyde/25 mol % propanal copolymer microcapsules. The photoresponsive shell provides a versatile polymer microcapsule technology for on-demand, controlled release of hydrophobic core payloads.

Unexpected Slow Relaxation Dynamics in Pure Ring Polymers Arise from Intermolecular Interactions.

Ring polymers have fascinated scientists for decades, but experimental progress has been challenging due to the presence of linear chain contaminants that fundamentally alter dynamics. In this work, we report the unexpected slow stress relaxation behavior of concentrated ring polymers that arises due to ring-ring interactions and ring packing structure. Topologically pure, high molecular weight ring polymers are prepared without linear chain contaminants using cyclic poly(phthalaldehyde) (cPPA), a metastable polymer chemistry that rapidly depolymerizes from free ends at ambient temperatures. Linear viscoelastic measurements of highly concentrated cPPA show slow, non-power-law stress relaxation dynamics despite the lack of linear chain contaminants. Experiments are complemented by molecular dynamics (MD) simulations of unprecedentedly high molecular weight rings, which clearly show non-power-law stress relaxation in good agreement with experiments. MD simulations reveal substantial ring-ring interpenetrations upon increasing ring molecular weight or local backbone stiffness, despite the global collapsed nature of single ring conformation. A recently proposed microscopic theory for unconcatenated rings provides a qualitative physical mechanism associated with the emergence of strong inter-ring caging which slows down center-of-mass diffusion and long wavelength intramolecular relaxation modes originating from ring-ring interpenetrations, governed by the onset variable N/ND, where the crossover degree of polymerization ND is qualitatively predicted by theory. Our work overcomes challenges in achieving ring polymer purity and by characterizing dynamics for high molecular weight ring polymers. Overall, these results provide a new understanding of ring polymer physics.

Densely Packed Tethered Polymer Nanoislands: A Simulation Study.

COordinated Responsive Arrays of Surface-Linked polymer islands (CORALS) allow for the creation of molecular surfaces with novel and switchable properties. Critical components of CORALs are the uniformly distributed islands of densely grafted polymer chains (nanoislands) separated by regions of bare surface. The grafting footprint and separation distances of nanoislands are comparable to that of the constituent polymer chains themselves. Herein, we characterize the structural features of the nanoislands and semiflexible polymers within to better understand this critical constituent of CORALs. We observe different characteristics of grafted semiflexible polymers depending on the polymer island's size and distance from the center of the island. Specifically, the characteristics of the chains at the island periphery are similar to isolated tethered polymer chains (full flexible chains), while chains in the center of the island experience the neighbor effect such as chains in the classic polymer brush. Chains close to the edge of the islands exhibit unique structural features between these two regimes. These results can be used in the rational design of CORALs with specific interfacial characteristics and predictable responses to external stimuli. It is hoped that this the discussion of the different morphologies of the polymers as a function of distance from the edge of the polymer will find applications in a wide variety of systems.

Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism.

Transient polymers rapidly and controllably depolymerize in response to a specific trigger, typically by a chain-end unzipping mechanism. Triggers, such as heat, light, and chemical stimuli, are generally dependent on the chemistry of the polymer backbone or end groups. Single electron transfer (SET), in contrast to other triggering mechanisms, is achievable by various means including chemical, electrochemical, and photochemical oxidation or reduction. Here, we identify SET and subsequent mesolytic cleavage as the major thermal triggering mechanism of cyclic poly(phthalaldehyde) (cPPA) depolymerization. Multimodal SET triggering is demonstrated by both chemical and photoredox-triggered depolymerization of cPPA. Redox-active small molecules (p-chloranil and 1,3,5-trimethoxybenzene) were used to tune the depolymerization onset temperature of cPPA over the range 105-135 °C. Extending this mechanism to photoredox catalysis, N-methylacridinium hexafluorophosphate (NMAPF6) was used to photochemically degrade cPPA in solution and thin films. Finally, we fabricated photodegradable cPPA monoliths with a storage modulus of 1.8 GPa and demonstrated complete depolymerization within 25 min of sunlight exposure. Sunlight-triggered depolymerization of cPPA is demonstrated and potentially useful for the manufacture of transient devices that vanish leaving little or no trace. Most importantly, this new mechanism is likely to inspire other SET-triggered transient polymers, whose development may address the ongoing crisis of plastic pollution.

Functionalized and Degradable Polyphthalaldehyde Derivatives.

Polymers that depolymerize back to monomers can be repeatedly chemically recycled, thereby reducing their environmental impact. Polyphthalaldehyde is a metastable polymer that can rapidly and quantitatively depolymerize due to its low ceiling temperature. However, the effect of substitution on the physical and chemical properties of polyphthalaldehyde derivatives has not been systematically studied. Herein, we investigate the cationic polymerization of seven o-phthalaldehyde derivatives and demonstrate that judicious choice of substituent results in materials with a wide range of ceiling temperatures (<-60 to 106 °C) and decomposition temperatures (109-196 °C). We anticipate that these new polymers and their derivatives will enable researchers to access degradable materials with tunable thermal, physical, and chemical properties.

Coordinated Responsive Arrays of Surface-Linked Polymer Islands-CORALs.

The concept of co-ordinated responsive arrays of surface-linked islands (polymer CORALs) is introduced. This study targets a responsive system capable of revealing or covering the substrate surface in response to environmental changes in a reversible way. A convenient method of fabrication of polymer CORALs is proposed. It is based on microphase separation that occurs in thin films of supramolecular assemblies of block copolymers with reactive blocks. Such blocks form nanometer-size domains that may serve as anchors for surface-linked polymer islands. Two characteristics of the islands are critically important for the switching function: high grafting density within the islands and small lateral separation that allows interactions between polymer chains grafted to the neighboring islands. This combination permits complete coverage of the substrate surface upon exposure to a good solvent (relaxed state). In a weak solvent, the chains collapse within the islands, thus revealing the substrate (compact state). The morphology of the CORALs in both states and some details of the switching process were studied with atomic force microscopy, grazing incidence small-angle scattering, and coarse-grained molecular dynamic simulations.