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 ... -  《-》

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 ... -  《-》

Folic acid-conjugated core/shell ZnS:Mn/ZnS quantum dots as targeted probes for two photon fluorescence imaging of cancer cells.

This work presents a novel approach to producing water soluble manganese-doped core/shell ZnS/ZnS quantum dots (ZnS:Mn/ZnS). The Mn-doped ZnS core was prepared through a nucleation doping strategy and a ZnS shell was grown on ZnS:Mn d-dots by decomposition of Zn(2+)-3-mercaptopropionic acid (MPA) complexes at 100 °C. It was found that the Mn2+(4)T1→6A1 fluorescence emission at ∼590 nm significantly increased after growth of the shell when the Mn2+ doping content was 4.0 at.%. A photoluminescence quantum yield of ∼22% was obtained for core/shell nanocrystals. The nanoparticles were structurally and compositionally characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and dynamic light scattering. The surface MPA molecules favor the dispersion of ZnS:Mn/ZnS QDs in aqueous media and make possible conjugation with targeting folic acid molecules. The folate receptor-mediated delivery of folic acid-conjugated ZnS:Mn/ZnS QDs was demonstrated using confocal microscopy with biphotonic excitation. Bare and folate-conjugated QDs exhibit only weak cytotoxicity towards folate receptor-positive T47D cancer cells and MCF-7 cells, used as a reference, at high concentrations (mmolar range) after 72h incubation.

Geszke M ，Murias M ，Balan L ，Medjahdi G ，Korczynski J ，Moritz M ，Lulek J ，Schneider R ... -  《-》

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 ... -  《-》

Sensitization enhancement of europium in ZnSe/ZnS core/shell quantum dots induced by efficient energy transfer.

Eu-doped ZnSe:/ZnS quantum dots (formed as ZnSe:Eu/ZnS QDs) were successfully synthesized by a two-step wet chemical method: nucleation doping and epitaxial shell growing. The sensitization characteristics of Eu-doped ZnSe and ZnSe/ZnS core/shell QD are studied in detail using photoluminescence (PL), PL excitation spectra (PLE) and time-resolved PL spectroscopy. The emission intensity of Eu ions is enhanced and that of ZnSe QDs is decreased, implying that energy was transferred from the excited ZnSe host materials (the donor) to the doped Eu ions (the acceptor). PLE reveals that the ZnSe QDs act as an antenna for the sensitization of Eu ions through an energy transfer process. The dynamics of ZnSe:Eu/ZnS core/shell quantum dots with different shell thicknesses and doping concentrations are studied via PL spectra and fluorescence lifetime spectra. The maximum phosphorescence efficiency is obtained when the doping concentration of Eu is approximately 6% and the sample showed strong white light under ultraviolet lamp illumination. By surface modification with ZnS shell layer, the intensity of Eu-related PL emission is increased approximately three times compared with that of pure ZnSe:Eu QDs. The emission intensity and wavelength of ZnSe:Eu/ZnS core/shell quantum dots can be modulated by different shell thickness and doping concentration. The results provide a valuable insight into the doping control for practical applications in laser, light-emitting diodes and in the field of biotechnology.

Liu N ，Xu L ，Wang H ，Xu J ，Su W ，Ma Z ，Chen K ... -  《-》