Cysteamine capped CdS quantum dots as a fluorescence sensor for the determination of copper ion exploiting fluorescence enhancement and long-wave spectral shifts.

We described a turn-on fluorescence sensor for the determination of Cu(2+) ions, utilizing the quantum confinement effect of cadmium sulfide quantum dots capped with cysteamine (Cys-CdS QDs). The fluorescence intensity of the Cys-CdS QDs was both enhanced and red shifted (from blue-green to yellow) in the presence of Cu(2+). Fluorescence enhancement was linearly proportional to the concentration of Cu(2+) in the concentration range 2 to 10µM. Other cations at the same concentration level did not significantly change the intensity and spectral maxima of Cys-CdS QDs, except Ag(+). The limit of detection was 1.5µM. The sensor was applied to the determination of Cu(2+) in (spiked) real water samples and gave satisfactory results, with recoveries ranging from 96.7 to 108.2%, and with RSDs ranging from 0.3 to 2.6%.

Cysteamine CdS quantum dots decorated with Fe3+ as a fluorescence sensor for the detection of PPi.

A new sensitive and selective fluorescence sensor for the detection of pyrophosphate (PPi) in aqueous media based on the Fe(3+) decorated cysteamine CdS QDs ([Cys-CdS QDs]-Fe(3+)) was proposed. The presence of PPi can induce the fluorescence quenching of [Cys-CdS QDs]-Fe(3+) due to the high formation constants between the phosphate group and Fe(3+). Because the complex between Fe(3+) and PPi acts as an efficient quencher, the concentration of PPi can be evaluated by tracking the degree of fluorescence quenching. The fabricated sensor was optimized to obtain the best sensor selectivity and sensitivity. Under optimal conditions, a linear relationship between the fluorescence response and the concentration of PPi was established in the range of 0.5-10 µM. The limits of detection and quantitation for PPi were found to be 0.11 and 2.78 µM, respectively. Furthermore, the proposed sensor exhibited high selectivity toward PPi relative to other common anions. The proposed sensor was successfully applied to the detection of PPi in urine samples with satisfactory results.

Cu2+-modulated cysteamine-capped CdS quantum dots as a turn-on fluorescence sensor for cyanide recognition.

A new fluorescence sensor for detection of cyanide ions (CN(-)) in aqueous media based on the recovered fluorescence of cysteamine capped CdS quantum dots [Cys-CdS QDs]-Cu(2+) system was proposed. The fluorescence intensity of Cys-CdS QDs was quenched by Cu(2+) due to the binding of Cu(2+) to cysteamine on the surface of the QDs. The degree of fluorescence quenching was proportional to the concentration of Cu(2+). However, in the presence of CN(-), the fluorescence intensity of Cys-CdS QDs was found to be efficiently recovered. Experimental results showed that the pH of the buffer solution and the concentration of Cu(2+) affected the fluorescence intensity upon adding CN(-). Under the optimal condition, the recovered fluorescence intensity was linearly proportional to the increasing CN(-) concentration in the range 2.5-20 µM. The limit of detection and the limit of quantification were found to be 1.13 µM and 3.23 µM, respectively. In addition, among the tested ions, only CN(-) could turn on the fluorescence intensity suggesting that the [Cys-CdS QDs]-Cu(2+) system was a highly selective sensor for CN(-). Moreover, this proposed sensor was demonstrated to detect CN(-) in drinking water with satisfactory results.

Determination of arsenic based on quenching of CdS quantum dots fluorescence using the gas-diffusion flow injection method.

A sequential injection analysis system for determination of arsenic based on hydride generation and fluorescence quenching of mercaptoacetic acid capped cadmium sulfide quantum dots (CdS-MAA QDs) is described. The generated arsine diffused across the PTFE membrane in a gas-diffusion unit and subsequently interacted with CdS-MAA QDs. The parameters affecting the arsine generation and the fluorescence quenching of QDs were studied. Under the optimum conditions, it was observed that a increase in the concentration of As(III) corresponded well to a decrease in fluorescence intensity according to the Stern-Volmer relationship. The extent of quenching was dependent on the concentration of arsenic in the range of 0.08-3.20 mmol L(-1), with the detection limit of 0.07 mg L(-1). The precision (%RSD) from eight replicates of the determination of As(III) 1.0 mg L(-1) was found to be 1.4%. The proposed method was applied to the determination of arsenic in ground water samples with satisfactory recoveries.

Enhancement of the fluorescence quenching efficiency of DPPH(•) on colloidal nanocrystalline quantum dots in aqueous micelles.

Luminescent CdS quantum dots capped with thioglycolic acid (CdS-TGA QDs) were demonstrated to serve as a fluorescence probe for a model organic radical, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•)), employing the quenching of the CdS-TGA QDs emission signal by the radical. Under the optimum conditions, the quenching efficiency of DPPH(•) on CdS-TGA QDs was proportional to the concentration of DPPH(•), following Stern-Volmer relationship. Different types of surfactants (cationic, anionic and neutral surfactants) were introduced to CdS-TGA QDs in order to increase the detection sensitivity. The fluorescence intensity of CdS-TGA QDs was greatly enhanced by cationic and neutral surfactants. Moreover, the quenching efficiency of DPPH(•) on the QDs in the presence of micelles was remarkably ca. 13 times higher than that in the system without micelles. Effects of pH and concentration of surfactants on the fluorescence quenching of CdS-TGA QDs were investigated. Electron spin resonance (ESR) spectroscopy was also used to monitor the DPPH radical species in CdS-TGA QDs mixtures with and without micelles. Fluorescence quenching mechanisms of CdS-TGA QDs by DPPH(•) in the presence and in the absence of CTAB were proposed.