Highly Fluorescent, Near-Infrared-Emitting Cd²⁺-Tuned HgS Nanocrystals with Optical Applications

Bulk HgS itself has proven to be a technologically important material; however, the poor stability and weak emission of HgS nanocrystals have greatly hindered their promising applications. Presently, a critical problem is the uncontrollable growth of HgS NCs and their intrinsic surface states which are susceptible to the local environment. Here, we address the issue by an ion-tuning approach to fabricating stable, highly fluorescent Cd:HgS/CdS NCs for the first time, which efficiently tuned the band-gap level of HgS NCs, pushing their intrinsic states far away from the surface, reducing the strong interaction of the environment with surface states and hence drastically boosting the exciton transition. As compared to bare HgS NCs, the obtained Cd:HgS/CdS NCs exhibited tunable luminescence peaks from 724 to 825 nm with an unprecedentedly high quantum yield up to 40% at room temperature and excellent thermal and photostability. Characterized by TEM, XRD, XPS, and AAS, the resultant Cd:HgS/CdS NCs possessed a zinc-blende structure and was composed of a homogeneous alloyed HgCdS structure coated with a thin-layer CdS shell. The formation mechanism of Cd:HgS/CdS NCs was proposed. These bright, stable HgS-based NCs presented promising applications as fluorescent inks for anticounterfeiting and as excellent light converters when coated onto a blue-light-emitting diode

Folate Receptor-Targeted and Cathepsin B‑Activatable Nanoprobe for <i>In Situ</i> Therapeutic Monitoring of Photosensitive Cell Death

The integration of diagnostic and therapeutic functions in a single system holds great promise to enhance the theranostic efficacy and prevent the under- or overtreatment. Herein, a folate receptor-targeted and cathepsin B-activatable nanoprobe is designed for background-free cancer imaging and selective therapy. The nanoprobe is prepared by noncovalently assembling phospholipid-poly­(ethylene oxide) modified folate and photosensitizer-labeled peptide on the surface of graphene oxide. After selective uptake of the nanoprobe into lysosome of cancer cells via folate receptor-mediated endocytosis, the peptide can be cleaved to release the photosensitizer in the presence of cancer-associated cathepsin B, which leads to 18-fold fluorescence enhancement for cancer discrimination and specific detection of intracellular cathepsin B. Under irradiation, the released photosensitizer induces the formation of cytotoxic singlet oxygen for triggering photosensitive lysosomal cell death. After lysosomal destruction, the lighted photosensitizer diffuses from lysosome into cytoplasm, which provides a visible method for <i>in situ</i> monitoring of therapeutic efficacy. The nanoprobe exhibits negligible dark toxicity and high phototoxicity with the cell mortality rate of 0.06% and 72.1%, respectively, and the latter is specific to folate receptor-positive cancer cells. Therefore, this work provides a simple but powerful protocol with great potential in precise cancer imaging, therapy, and therapeutic monitoring