Highly Efficient Room-Temperature Light-Induced Synthesis of Polymer Dots: A Programming Control Paradigm of Polymer Nanostructurization from Single-Component Precursor

Abstract

Polymer dots (PDs) have raised considerable research interest due to their advantages of designable nanostructures, high biocompatibility, versatile photoluminescent properties, and recyclability as nanophase. However, there remains a lack of in situ, real-time, and noncontact methods for synthesizing PDs. Here we report a rational strategy to synthesize PDs through a welldesigned single-component precursor (an asymmetrical donor− acceptor−donor′ molecular structure) by photoirradiation at ambient temperature. In contrast to thermal processes that normally lack atomic economy, our method is mild and successive, based on an aggregation-promoted sulfonimidization triggered by photoinduced delocalized intrinsic radical cations for polymerization, followed by photooxidation for termination with structural shaping to form PDs. This synthetic approach excludes any external additives, rendering a conversion rate of the precursor exceeding 99%. The prepared PDs, as a single entity, can realize the integration of nanocore luminescence and precursor-transferred luminescence, showing 41.5% of the total absolute luminescence quantum efficiency, which is higher than most reported PD cases. Based on these photoluminescent properties, together with the superior biocompatibility, a unique membrane microenvironmental biodetection could be exemplified. This strategy with programming control of the single precursor can serve as a significant step toward polymer nanomanufacturing with remote control, high-efficiency, precision, and real-time operability.

Coupled Poly(ethylenimine) Coreactant to Enhance Electrochemiluminescence of Polymer Dots for Array Imaging of Protein Biomarkers

“…Polymer dots (Pdots), as a type of emerging ECL emitters, have attracted much attention due to their excellent biocompatibility, nontoxicity, easy modification, and tunable luminescent properties. − To boost the ECL efficiency of Pdots, which is relatively lower than those of inorganic luminescent materials, for sensitive bioimaging analysis, our previous works sequentially proposed some strategies by introducing electron-withdrawing groups, donor–acceptor pairs, or aggregation-induced emission active moieties into the molecular structures to promote the electron or energy transfer. Unfortunately, these strategies still suffer from some deficiencies, such as the complexity and low yield of Pdots, multistep modification reactions, and the necessity for excessive exogenous coreactants, which may have long-term adverse effects on the aquatic environment and organisms.…”