Closed-Loop Polymer-to-Polymer Upcycling of Waste Poly (Ethylene Terephthalate) into Biodegradable and Programmable Materials.

Poly(ethylene terephthalate) (PET), extensively employed in bottles, film, and fiber manufacture, has generated persistent environmental contamination due to its non-degradable nature. The resolution of this issue requires the conversion of waste PET into valuable products, often achieved through depolymerization into monomers. However, the laborious purification procedures involved in the extraction of monomers pose challenges and constraints on the complete utilization of PET. Herein, a strategy is demonstrated for the polymer-to-polymer upcycling of waste PET into high-value biodegradable and programmable materials named PEXT. This process involves reversible transesterifications dependent on ester bonds, wherein commercially available X-monomers from aliphatic diacids and diols are introduced, utilizing existing industrial equipment for complete PET utilization. PEXT features a programmable molecular structure, delivering tailored mechanical, thermal, and biodegradation performance. Notably, PEXT exhibits superior mechanical performance, with a maximal elongation at break of 3419.2 % and a toughness of 270.79 MJ m-3. These characteristics make PEXT suitable for numerous applications, including shape-memory materials, transparent films, and fracture-resistant stretchable components. Significantly, PEXT allows closed-loop recycling within specific biodegradable analogs by reprograming PET or X-monomers. This strategy not only offers cost-effective advantages in large-scale upcycling of waste PET into advanced materials but also demonstrates its enormous prospect in environmental conservation.

Reduction-Responsive Anticancer Nanodrug Using a Full Poly(ethylene glycol) Carrier.

Poly(ethylene glycol) (PEG) is applied extensively in biomedical fields because of its nontoxic, nonimmunogenic, and protein resistance properties. However, the strong hydrophilicity of PEG prevents it from self-assembling into an amphiphilic micelle in water, making it a challenge to fabricate a full-PEG carrier to deliver hydrophobic anticancer drugs. Herein, a paclitaxel (PTX)-loaded nanodrug was readily prepared through self-assembly of PTX and an amphiphilic PEG derivative, which was synthesized via melt polycondensation of two PEG diols (i.e., PEG200 and PEG10k) and mercaptosuccinic acid. The full PEG component endows the nanocarrier with good biocompatibility. Furthermore, because of the core cross-linked structure via the oxidation of mercapto groups, the nanodrug can be selectively disassociated under an intratumor reductive microenvironment through the reduction of disulfide bonds to release the loaded PTX and kill the cancer cells while maintaining high stability under the extratumor physiological condition. Additionally, it was confirmed that the nanodrug not only prolongs the biocirculation time of PTX but also possesses excellent in vivo antitumor efficacy while avoiding side effects of free PTX, for example, liver damage, which is promising for delivering clinical hydrophobic drugs to treat a variety of malignant tumors.

Full Poly(ethylene glycol) Hydrogels with High Ductility and Self-Recoverability.

Energy dissipation is a common mechanism to improve the ductility of polymeric hydrogels. However, for poly(ethylene glycol) (PEG) hydrogels, it is not easy to dissipate energy, as polymer chains are dispersed in water without strong interchain interactions or decent entanglement. The brittleness limits the real applications of PEG hydrogels, although they are promising candidates in biomedical fields, as PEG has been approved by the U.S. Food and Drug Administration. Herein, we chemically introduced a center for energy dissipation in the PEG hydrogel system. Amphiphilic segmented PEG derivatives were designed through the melt polycondensation of triethylene glycol (PEG150) and high molecular weight PEG in the presence of succinic acid and mercaptosuccinic acid as dicarboxylic acids. Full PEG hydrogels with elastic nanospheres as giant cross-linkers were facilely prepared by the self-assembly of esterified PEG150 segments and the oxidation of mercapto groups. The resultant full PEG hydrogels can dissipate energy by the deformation of elastic nanospheres with outstanding ductility and self-recoverability while maintaining the excellent biocompatibility owing to their full PEG components. This work provides an original strategy to fabricate full PEG hydrogels with high ductility and self-recoverability, potentially applicable in biomedical fields.