Water-soluble luminescent CdS quantum dots (QDs) capped by polyphosphate, L-cysteine, and thioglycerol were synthesized in aqueous solution. The ligands were found to have a profound effect on the luminesence response of CdS QDs to physiologically important metal cations. Polyphosphate-capped CdS QDs were sensitive to nearly all mono- and divalent cations, showing no ion selectivity. Conversely, thioglycerol-capped CdS QDs were sensitive to only copper and iron ions. Similar concentrations of physiologically relevant cations, such as zinc, sodium, potassium, calcium, and magnesium ions did not affect the luminescence of thioglycerol-capped CdS QDs. On the other hand, L-cysteine-capped CdS QDs were sensitive to zinc ions and insensitive to other physiologically important cations, such as copper, calcium, and magnium ions. To demonstrate the detection capability of these new ion probes, L-cysteine and thioglycerol-capped CdS QDs were used to detect zinc and copper ions in physiological buffer samples. The detection limits were 0.8 microM for zinc (II) and 0.1 microM for copper (II) ions. The emission enhancement of the QDs by zinc (II) is attributed to activation of surface states, whereas the effective reduction of copper (II) to copper (I) may explain the emission decrease of the thioglycerol-capped CdS QDs when charged with copper ions. Unlike organic fluorescent dyes, the thioglycerol-capped luminescent CdS QDs discriminate between copper and zinc ions and are therefore suitable for the analysis of copper ions in biological samples in the presence of physiological concentrations of zinc ions. The interference of iron ions with zinc and copper ion detection is attributed to an inner filter effect, which is eliminated by adding fluoride ions to form the colorless complex FeF6(3-). To the best of our knowledge, this is first use of luminescent semiconductor quantum dots as selective ion probes in aqueous samples.
This paper describes the synthesis of new nanocomposite nanoparticles that consist of polymer coated γ-Fe2O3 superparamagnetic cores and CdSe/ZnS quantum dots (QDs) shell. A single layer of QDs was bound to the surface of thiol-modified magnetic beads through the formation of thiol−metal bonds to form luminescent/magnetic nanocomposite particles. Transmission electron microscopy (TEM) and energy disperse spectroscopy (EDS) were used to characterize the size, size distribution, and composition of the luminescent/magnetic nanoparticles. Their average diameter was 30 nm with a size variation of ±15%. The nanoparticles were modified with carboxylic groups to increase their miscibility in aqueous solution. A 3-fold decrease in the luminescence quantum yield of the luminescent/magnetic particles and a slight blue shift in their emission peaks compared to individual luminescent QDs were observed. However, the particles were bright and were easily observed using a conventional fluorescence microscope. Additionally, no apparent broadening of the luminescence peak of the QDs could be seen. The luminescent/magnetic nanoparticles were easily separated from solution by magnetic decantation using a permanent magnet. The new particles could be used in a variety of bioanalytical assays involving luminescence detection and magnetic separation. To demonstrate their utility we immobilized anticycline E antibodies on their surface and used the antibody coated particles to separate MCF-7 breast cancer cells from serum solutions. Anticycline E antibodies bind specifically to cycline, a protein which is specifically expressed on the surface of breast cancer cells. The separated breast cells were easily observed by fluorescence imaging microscopy due to the strong luminescence of the luminescent/magnetic nanocomposite particles.
A unique, sensitive, and highly specific immunoassay system for antibodies using gold nanoparticles has been developed. The assay is based on the aggregation of gold nanoparticles that are coated with protein antigens in the presence of their corresponding antibodies. The aggregation of the gold nanoparticles results in an absorption change at 620 nm that is monitored using an absorption plate reader. To demonstrate the analytical capabilities of the new technique, monodispersed protein A-coated gold particles, averaging 10 nm in diameter, were used to determine the level of anti-protein A in serum samples. The effects of the pH, the temperature, and the concentration of protein A-coated gold nanoparticles on the sensitivity of the assay were investigated using transmission electron microscopy (TEM) and UV/vis absorption spectroscopy. A dynamic range of 2 orders of magnitude and a limit of detection of 1 microg/mL of anti-protein A were observed. The new technique could be used for fast, high-throughput screening of antibodies in clinical diagnostic applications.
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