Aqueous synthesis of Ag and Mn co-doped In(2)S(3)/ZnS quantum dots with tunable emission for dual-modal targeted imaging.

Here, we present the microwave-assisted synthesis of In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ altered the optical properties of the host QDs, whereas the spin magnetic moment (S=5/2) of Mn2+ efficiently induced the longitudinal relaxation of water protons. To the best of our knowledge, this is the first report of the aqueous synthesis of color-tunable AgMn:In2S3/ZnS core/shell QDs with magnetic properties. The synthetic procedure is rapid, facile, reproducible, and scalable. The obtained QDs offered a satisfactory quantum yield (45%), high longitudinal relaxivity (6.84s-1mM-1), and robust photostability. In addition, they exhibited excellent stability over a wide pH range (5-12) and high ionic strength (0.15-2.0M NaCl). As seen by confocal microscopy and magnetic resonance imaging, AgMn:In2S3/ZnS conjugated to hyaluronic acid (referred to as AgMn:In2S3/ZnS@HA) efficiently and specifically targeted cluster determinant 44, a receptor overexpressed on cancer cells. Moreover, AgMn:In2S3/ZnS@HA showed negligible cytotoxicity in vitro and in vivo, rendering it a promising diagnostic probe for dual-modal imaging in clinical applications. In this manuscript, we reported a facial and rapid method to prepare In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ dopants were used to alter the optical properties of the In2S3 host, whereas Mn2+ co-dopants with their unpaired electrons provided paramagnetic properties. The emission wavelength of the core/shell QDs could be tuned from 550 to 743nm with a maximum PL quantum yield of 45%. The resulting core/shell QDs also maintained a stable emission in aqueous solution at broad ranges of pH (5-12) and ionic strength (0.15-2.0M NaCl), as well as a high photostability under continuous irradiation. In vivo cytotoxicity experiments showed that up to 500μg/mL AgMn:In2S3/ZnS@HA did not cause obvious toxicity to zebrafish embryos. In vitro targeted cell luminescence and magnetic resonance imaging showed that AgMn:In2S3/ZnS conjugated to hyaluronic acid was selectively and efficiently internalized in CD44-expressing tumor cells, confirming that the resultant QDs could function as dual-modal imaging probes for accurate diagnosis.

Lai PY ，Huang CC ，Chou TH ，Ou KL ，Chang JY ... -  《-》

Colloidal synthesis of tunably luminescent AgInS-based/ZnS core/shell quantum dots as biocompatible nano-probe for high-contrast fluorescence bioimaging.

Tremendous demands for simultaneous imaging of biological entities, along with the drawback of photobleaching in fluorescent dyes, have encouraged scientists to apply novel and non-toxic colloidal quantum dots (QDs) in biomedical researches. Herein, a novel aqueous-phase approach for the preparation of multicomponent In-based QDs is reported. Absorption and photoluminescence emission spectra of the as-prepared QDs were tuned by alteration of QDs' composition as Zn-Ag-In-S/ZnS, Ag-In-S/ZnS and Cu-Ag-In-S/ZnS core/shell QDs. In order to reach reproducibly intense and tunable light-emissive colloidal QDs with green, amber, and red color, various optimization steps were carefully performed. The structural characterizations such as EDX, ICP-AES, XRD, TEM and FT-IR measurements were also carried out to demonstrate the success of the present method to prepare extremely quantum-confined QDs capped with functional groups. Then, to ensure their promising biomedical applications, the generated intracellular reactive oxygen species (ROS) by QDs were quantitatively and qualitatively measured in dark conditions and under 405 nm laser irradiation. Our results verified an enhancement in the generation of reactive oxygen species (ROS) and cytotoxic effects in the presence of laser irradiation while their muted toxic effects in dark conditions confirmed biocompatible properties of un-excited In-based QDs. Moreover, bioimaging analysis revealed strong merits of the suggested synthetic route to achieve ideal fluorescent QDs as bright/multi-color optical nano-probes in imaging and transporting pumps in the cell membrane. This further emphasized the potential ability of the present AgInS-based/ZnS QDs in obtaining required results as theranostic agents for simultaneous treatment and imaging of cancer. The harmonized advantages in simplicity and effectiveness of synthesis procedure, excellent structural/optical properties enriched with confirmed biomedical merits in high contrast imaging and potential treatment highlight the present work.

Soheyli E ，Ghaemi B ，Sahraei R ，Sabzevari Z ，Kharrazi S ，Amani A ... -  《-》

Synthesis and Characterization of Mn:ZnSe/ZnS/ZnMnS Sandwiched QDs for Multimodal Imaging and Theranostic Applications.

In this work, a facile aqueous synthesis method is optimized to produce Mn:ZnSe/ZnS/ZnMnS sandwiched quantum dots (SQDs). In this core-shell co-doped system, paramagnetic Mn(2+) ions are introduced as core and shell dopants to generate Mn phosphorescence and enhance the magnetic resonance imaging signal, respectively. T1 relaxivity of the nanoparticles can be improved and manipulated by raising the shell doping level. Steady state and time-resolved optical measurements suggest that, after high level shell doping, Mn phosphorescence of the core can be sustained by the sandwiched ZnS shell. Because the SQDs are free of toxic heavy metal compositions, excellent biocompatibility of the prepared nanocrystals is verified by in vitro MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay. To explore the theranostic applications of SQDs, liposome-SQD assemblies are prepared and used for ex vivo optical and magnetic resonance imaging. In addition, these engineered SQDs as nanocarrier for gene delivery in therapy of Panc-1 cancer cells are employed. The therapeutic effects of the nanocrystals formulation are confirmed by gene expression analysis and cell viability assay.

Wang Y ，Wu B ，Yang C ，Liu M ，Sum TC ，Yong KT ... -  《-》

Aqueous synthesis of highly luminescent glutathione-capped Mn²⁺-doped ZnS quantum dots.

In this paper, an aqueous-based route has been developed to prepare highly luminescent glutathione (GSH)-capped Mn-doped ZnS quantum dots (QDs). The dots obtained have an average diameter of 4.3 nm and exhibit the Mn(2+)-related orange luminescence with very low surface defect density. The highest photoluminescence was observed for a Mn(2+) to Zn(2+) molar ratio of 3%. Consecutive overcoating of the Mn:ZnS@GSH QDs by a ZnS shell was done, and the core/shell structured QDs exhibit a PL quantum yield of 23%. Transmission electron microscopy, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy, UV-visible spectroscopy and spectrofluorometry have been used to characterize the crystal structure, the doping status, and the optical properties of the doped-QDs. Our systematic investigation shows that Mn:ZnS/ZnS@GSH QDs are highly promising fluorescent labels in biological applications.

Kolmykov O ，Coulon J ，Lalevée J ，Alem H ，Medjahdi G ，Schneider R ... -  《-》

Tunable excitation properties of ZnCdS:Mn/ZnS quantum dots for cancer imaging.

Water-soluble ZnS:Mn quantum dots (QDs) were synthesized using a hydrothermal method with 3-mercaptopropionic acid as stabilizer. The optical properties of ZnS:Mn QDs were thoroughly investigated by tuning the doping concentration of Mn2+ and the Zn/S precursor ratio, to obtain an optimal parameter for QDs with excellent fluorescence characteristics. ZnS:Mn QDs excited at only one wavelength, however, which seriously limited their further application. Here, a trace Cd ion was doped into a ZnS host, resulting in QD excitation covering a wide adjustable waveband. Furthermore, when a ZnS shell was coated onto the surface of the ZnCdS:Mn QDs, photoluminescence intensity and stability were further enhanced. After coupling with an anti-CK 19 antibody, the ZnCdS:Mn/ZnS core/shell QDs were able to function by labeling cancer cells, indicating that they could be considered as a suitable bio-probe for cells and tissue imaging.

Yin N ，Liu L ，Li P ，Zhao S ... -  《-》