A new type of fluorescent material is presented, which is called non-conjugated polymer dots (NCPDs). The NCPDs only possess sub-fluorophores (which are groups such as C=O, C=N, N=O) instead of typical conjugated fluorophore groups, and thus these materials should not have strong photoluminescence (PL) in the usual sense. Nevertheless, the PL of these sub-fluorophores can be enhanced by chemical crosslinking or physical immobilization of polymer chains, which is named the crosslink-enhanced emission (CEE) effect. The significant advances achieved by us and other groups on both experimental and theoretical aspects are discussed, and the covalent-bond CEE, rigidity-aggregated CEE, or supramolecular CEE in NCPDs is elaborated. Moreover, synthetic strategies, unique optical properties, and the promise of NCPDs in bio-related fields, such as bioimaging and drug delivery, are systematically discussed.
The crosslink enhanced emission (CEE) in a new type of non-conjugated polymer dots (PDs) is proved. The enhanced PL originates from the decreased vibration and rotation of amino-based chromophores. Furthermore, the cellular uptake mechanism and internalization of PDs were investigated in detail.
Carbon dots (CDs) are novel fluorescent materials with low toxicity and good biocompatibility. Herein, the collisional/dynamic and photoluminescence (PL) center destruction quenching behaviors of a novel type of CDs were investigated. Moreover, the quenching behaviors of the CDs were exploited in applications. Firstly, dynamic PL quenching was achieved by Fe(3+) ions, which was proved by the Stern-Volmer equation, temperature dependent quenching and fluorescence lifetime measurements. Furthermore, a hemin sensor based on the Fe(3+)/CDs system was achieved. Secondly, quenching induced by PL center destruction was caused by hydroxyl radicals (˙OH), which were produced by high power UV light or the H2O2/Fe(2+) system; thus an H2O2 sensor with a low detection limit (0.9 ppb) was realized. Finally, we assumed that the CDs are really composed of cross-linked molecular clusters, and that the PL centers of the as prepared CDs are certain molecular/chemical groups.
Nanomedicines have achieved several breakthroughs in cancer treatment over the past decades; however, their potential immunotoxicities are ignored, which results in serious adverse effects and greatly reduces the potential in clinical translation. Herein, we innovatively develop a theranostic supramolecular polymer using β-cyclodextrin as the host and camptothecin (CPT) as the guest linked by a glutathione-cleavable disulfide bond. The supramolecular polymerization remarkably increases the solubility of CPT by a factor of 232 and effectively inhibits its lactone ring opening in physiological environment, which is favorable for intravenous formulation and maintenance of the therapeutic efficacy. Supramolecular nanoparticles can be prepared through orthogonal self-assembly driven by π-π stacking interaction, host-guest complexation, and hydrogen bonds. The sophisticated nanomedicine constructed from the obtained supramolecular polymer can be specifically delivered to tumor sites and rapidly excreted from body after drug release, thus effectively avoiding systemic toxicity, especially long-term immunotoxicity. In vivo investigations demonstrate this supramolecular nanomedicine possesses superior antitumor performance and antimetastasis capability. This pioneering example integrating the advantages of the dynamic nature of supramolecular chemistry and nanotechnology provides a promising platform for cancer theranostics.
A universal route to GQDs is developed based on "solution phase-based scissor" methods. The PL centers of the GQDs are systematically studied and are proved to be the surface state. This is related to the hybridization structure of the edge groups and the connected partial graphene core. Through experiment and analysis, we have preliminarily proved that the efficient edge groups for green emission are mainly carboxyl, carbonyl and amide. This is indicated by the following three factors: firstly, the PL of GQDs is enhanced by UV exposure, during which partial -OH groups are converted into carboxyl groups; secondly, the PL properties of GQDs can be further improved by one-step solvothermal treatment, in which partial carboxyl groups are converted to amide groups and the surface state of the GQDs is enhanced; thirdly, reduced m-GQDs possess more -OH groups compared with reduced GQDs, resulting in more blue PL centers (the carboxyl, carbonyl and amide-based green centers are converted to -OH-based blue centers). The present work highlights a very important direction for the understanding of the PL mechanism of GQDs and other related carbon-based materials.
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