In this work, we designed and fabricated a nanoscopic sugar-based magnetic hybrid material that is capable of tackling environmental pollution posed by marine oil spills, while minimizing potential secondary problems that may occur from microplastic contamination. These readily-defined magnetic nanocomposites were constructed through co-assembly of magnetic iron oxide nanoparticles (MIONs) and a degradable amphiphilic polymer, poly(ethylene glycol)- b -dopamine-functionalized poly(ethyl propargyl glucose carbonate)- b -poly(ethyl glucose carbonate), PEG- b -PGC[(EPC-MPA)- co -(EPC-DOPA)]- b -PGC(EC), driven by supramolecular co-assembly in water with enhanced interactions provided via complexation between dopamine and MIONs. The composite nanoscopic assemblies possessed a pseudo -micellar structure, with MIONs trapped within the polymer framework. The triblock terpolymer was synthesized by sequential ring-opening polymerizations (ROPs) of two glucose-derived carbonate monomers, initiated by a PEG macroinitiator. Dopamine anchoring groups were subsequently installed by first introducing carboxylic acid groups using a thiol–yne click reaction, followed by amidation with dopamine. The resulting amphiphilic triblock terpolymers and MIONs were co-assembled to afford hybrid nanocomposites using solvent exchange processes from organic solvent to water. In combination with hydrophobic interactions, the linkage between dopamine and iron oxide stabilized the overall nanoscopic structure to allow for the establishment of a uniform globular morphology, whereas attempts at co-assembly with the triblock terpolymer precursor, lacking dopamine side chains, failed to afford well-defined nanostructures. The magnetic hybrid nanoparticles demonstrated high oil sorption capacities, ca. 8 times their initial dry weight, attributed, in part, to large surface areas leading to effective contact between the nanomaterials and hydrocarbon pollutants. Moreover, the naturally-derived polymer framework undergoes hydrolytic degradation to break down into byproducts that include glucose, ethanol and dopamine if not recovered after deployment, alleviating concerns of potential microplastic generation and persistence.
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Glucose‐derived superabsorbent hydrogel materials based on mechanically‐interlocked slide‐ring and triblock copolymer topologies
A series of glucose‐based degradable superabsorbent hydrogels with potential to tackle issues associated with sustainability, flooding, and drought has been designed and fabricated. These hydrophilic networks were constructed through integrating glucose as a primary building block –into cyclic oligomers and block polymers, which were combined into mechanically‐interlocked slide‐ring crosslinked materials. Crosslinking of slide ring α‐cyclodextrin/poly(ethylene glycol)‐type polyrotaxanes with acid‐functionalized ABA triblock copolymers comprised of mercaptopropionic acid‐functionalized poly(glucose carbonate (ethyl propargyl carbonate))‐
- Award ID(s):
- 1905818
- NSF-PAR ID:
- 10389087
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Polymer Science
- Volume:
- 61
- Issue:
- 10
- ISSN:
- 2642-4150
- Format(s):
- Medium: X Size: p. 937-950
- Size(s):
- ["p. 937-950"]
- Sponsoring Org:
- National Science Foundation
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Abstract Clinical application of injectable, thermoresponsive hydrogels is hindered by lack of degradability and controlled drug release. To overcome these challenges, a family of thermoresponsive, ABC triblock polymer‐based hydrogels has been engineered to degrade and release drug cargo through either oxidative or hydrolytic/enzymatic mechanisms dictated by the “A” block composition. Three ABC triblock copolymers are synthesized with varying “A” blocks, including oxidation‐sensitive poly(propylene sulfide), slow hydrolytically/enzymatically degradable poly(ε‐caprolactone), and fast hydrolytically/enzymatically degradable poly(
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Ring-sliding behavior in polyrotaxanes imbues gels, elastomers, and glasses with remarkable stress-dissipation and actuation properties. Since these properties can be modulated and tuned by structural parameters, many efforts have been devoted to developing synthetic protocols that define the structures and properties of slide-ring materials. We introduce post-synthetic modifications of slide-ring gels derived from unmodified α-cyclodextrin and poly(ethylene glycol) polyrotaxanes that enable (i) actuation and control of the thermo-responsive lower critical solution temperature (LCST) behavior of ring-modified slide-ring hydrogels, and (ii) chemically bonding separate gels into hybrid or shape-reconfigured macro-structures with a slide-ring adhesive solution. The mechanical properties of the post-modified gels have been characterized by shear rheology and uniaxial tensile tests, while the corresponding xerogels were characterized by wide-angle X-ray scattering. These demonstrations show that post-synthetic modification offers a practical solution for re-configuring the properties and shapes of slide-ring gels.more » « less
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