[Show abstract][Hide abstract] ABSTRACT: Cytotoxicity tests of zinc sulfide (ZnS) and cadmium sulfide (CdS) quantum dots (QDs) synthesized via all-aqueous process with various surface conditions were carried out with human endothelial cells (EA hy926) using two independent viability assays, i.e., by cell counting following Trypan blue staining and by measuring Alamar Blue (AB) fluorescence. The ZnS QDs with all four distinct types of surface conditions were nontoxic at both 1 microM and 10 microM concentrations for at least 6 days. On the other hand, the CdS QDs were nontoxic only at 1 microM, and showed significant cytotoxicity at 10 microM after 3 days in the cell counting assay and after 4 days in the AB fluorescence assay. The CdS QDs with (3-mercaptopropyl)trimethoxysilane (MPS)-replacement plus silica capping were less cytotoxic than those with 3-mercaptopropionic acid (MPA) capping and those with MPS-replacement capping. Comparing the results of ZnS and CdS QDs with the same particle size, surface condition and concentration, it is indicated that the cytotoxicity of CdS QDs and the lack of it in ZnS QDs were probably due to the presence and absence of the toxic Cd element, respectively. The nontoxicity of the aqueous ZnS QDs makes them favorable for in vivo imaging applications.
Journal of Nanoscience and Nanotechnology 04/2011; 11(4):3543-51. DOI:10.1166/jnn.2011.3803 · 1.56 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: We report an all-aqueous synthesis of highly photoluminescent and stable ZnS quantum dots (QDs) with water as the medium, i.e. first synthesizing ZnS QDs with 3-mercaptopropionic acid (MPA) as the capping molecule, followed by replacing some of MPA with (3-mercaptopropyl) trimethoxysilane (MPS). The resultant MPS-replaced ZnS QDs were about 5 nm in size with a cubic zinc blende crystalline structure, and had both MPA and MPS on the surface as confirmed by the Fourier Transform Infrared (FTIR) spectroscopy. They exhibited blue trap-state emissions around 415 nm and a quantum yield (QY) of 75% with Rhodamine 101 as the reference, and remained stable for more than 60 days under the ambient conditions. Through the capping molecule replacement procedure, the MPS-replaced ZnS QDs avoided the shortcomings of both the MPA-ZnS QDs and the MPS-ZnS QDs, and acquired the advantages of strong photoluminescence and good stability, which are important to the QDs' applications especially for bioimaging.
[Show abstract][Hide abstract] ABSTRACT: In this study, we have examined the transfection of aqueous CdS quantum dots (QDs) in the cytoplasm of PC12 neuronal cells using polyethylenimine (PEI) as carrier. The CdS QDs were prepared using a unique aqueous synthesis method, at 5 nm in size and capped with 3-mercaptopropyltrimethoxysilane (MPS). They exhibited a quantum yield of 7.5% and a zeta potential of -25 mV. With PEI they formed complexes by electrostatic attraction. At PEI/QD number ratios of>100, the PEI-QD complexes obtained exhibited a saturated size of about 24 nm and a zeta potential of about 15 mV. Confocal microscopy showed that PEI-QD complexes of a PEI/QD number ratio of 200 were successfully internalized and uniformly distributed inside the cells, indicating that the PEI-QD complexes were able to rupture the vesicles to enter the cytoplasm without aggregation. In addition, we showed that the presence of the PEI did not reduce the photoluminescence of the QDs and only mildly reduced the mitochondrial activity of the transfected cells-with no apparent reduction at a PEI/QD ratio of <40 to about 30% reduction at a PEI/QD number ratio of 200.
[Show abstract][Hide abstract] ABSTRACT: We have examined the synthesis and stability of ZnS quantum dots (QDs) using an all-aqueous route at pH = 12 with (3-mercaptopropyl)trimethoxysilane (MPS) as the capping molecule. The MPS-capped ZnS QDs obtained were well dispersed with a particle size around 5 nm and a cubic zinc blende crystalline structure. The QDs exhibited optimal photoluminescence (PL) emission when the MPS:Zn:S ratio was between 1/4:2:1 and 1/2:2:1. Compared with the earlier obtained ZnS QDs capped with 3-mercaptopropionic acid (MPA), the MPS-capped ZnS QDs exhibited a similar, high quantum yield, 42% and 25% for MPS:Zn:S 1/2:2:1 and 1/4:2:1, respectively, but much better photostability. With the MPS:Zn:S ratio of 1/4:2:1, we showed that at room temperature and under the normal laboratory lighting conditions, the MPS-capped QDs were able to maintain their PL intensity for more than 50 days without degradation. We further showed that the MPS-capped QDs were stable not only in their synthesis solution but also in deionized (DI) water and in phosphate buffer saline (PBS) solution. The QDs with 1/2:2:1 were able to stay at 50 degrees C for more than 20 h without degrading the PL intensity. They were also stable under continuous UV exposure for 3 h. With the high quantum yield and significantly improved photostability, the MPS-capped ZnS QDs could be good imaging tools for many biological applications.
[Show abstract][Hide abstract] ABSTRACT: We have examined the aqueous synthesis of non-heavy-metal ZnS quantum dots (QDs) using 3-mercaptopropionic acid (MPA) as the capping molecule at various pH and MPA:Zn:S ratios. Transmission electron microscopy (TEM) and x-ray diffraction (XRD) indicated that the aqueous ZnS QDs were 3–5 nm in size with a zinc blende structure. We showed that, at pH 12 with a MPA:Zn:S = 8:4:1 ratio, the ZnS QDs with optimal blue emission could be obtained in a one-step, room-temperature aqueous process that exhibited a quantum yield of 31%, higher than that of the commercial CdSe/ZnS core–shell QDs. The present ZnS QDs could pass through a 50 kD filter. This indicated that they were smaller than 5 nm in size, consistent with those estimated from the UV–vis absorption edge and the TEM image. At a lower pH (e.g. pH = 8), the room-temperature synthesized ZnS QDs exhibited no photoluminescence. Although further hydrothermal annealing at 100 ◦C could improve the photoluminescence of the ZnS QDs, the resultant emission was not as bright as that obtained at pH 12 at room temperature. The blue emission of aqueous ZnS QDs was likely the result of trap-state emissions involving the defect states of the QDs. The present ZnS QDs were bright, small and contained non-heavy-metal elements, thus offering the potential for in vivo bioimaging.
[Show abstract][Hide abstract] ABSTRACT: A direct and environmentally friendly synthesis method was developed to produce aqueous CdS quantum dots (QDs) at room temperature. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) results showed the small size and the cubic zinc blende structure of the nanocrystals. The quantum yield was comparable to that of the commercial core-shell QDs. With 3-mercaptopropionic acid (MPA) as the capping molecule, the feasibility of using the aqueous CdS QDs as imaging tool was demonstrated with Salmonella typhimurium cells. The photoluminescence (PL) properties of the present aqueous CdS QDs can be optimized by adjusting various processing parameters. The emission was due to trap states and was related to the dispersion condition. In particular, with higher pH and MPA/Cd ratio of 2, the QDs exhibited stronger emission. The temperature-and concentration-dependent properties of QDs resulted from the intrinsic interactions between nanoparticles. The aqueous CdS QDs displayed long lifetime of 12 h under UV light and excellent stability in DI water, PBS, and cytosol for more than 26 days. The ease of processing and good PL properties of the aqueous CdS QDs provide a practical and economical approach for single-target imaging application.
[Show abstract][Hide abstract] ABSTRACT: Item from the Biomedical Technology Showcase held July 20, 2006 at Drexel University's Bossone Research Enterprise Center. Quantum dots (QDs) are semiconductor nanocrystals that exhibit distinctive photoluminescence properties due to the quantum confinement effect. We have developed a unique aqueous synthesis route to produce highly luminescent non-heavy metal ZnS QDs capped with carboxylated molecules in one single step. They differ from commercial quantum dots in that they do not contain toxic heavy metals and that they are very small, ideal for invivo biomarker applications. The carboxyl-capped QDs are 2-5 nm in size, biologically-benign, stable, and ready for conjugation with proteins or other biomolecules as fluorescence markers for molecular tracking and disease diagnoses.