Ascorbic Acid Induced Enhancement of Room Temperature Phosphorescence of Sodium Tripolyphosphate-Capped Mn-Doped ZnS Quantum Dots: Mechanism and Bioprobe Applications

• Published in: Chemistry : a European journal 2010-11, Vol.16 (43), p.12988-12994
• Main Authors: Wang, He-Fang, Li, Yan, Wu, Ye-Yu, He, Yu, Yan, Xiu-Ping
• Format: Article
• Language: English
• Subjects: Ascorbic acid; Ascorbic Acid - analysis; Ascorbic Acid - blood; Ascorbic Acid - chemistry; Ascorbic Acid - urine; Biological; Biosensing Techniques; Chemistry; Excitation; Humans; Luminescent Measurements; Manganese; Manganese - chemistry; Molecular Structure; Phosphatidylethanolamines; Phosphorescence; Polyphosphates - chemistry; Quantum Dots; sensors; Sodium; sodium tripolyphosphate; Sulfides - chemistry; Temperature; Zinc Compounds - chemistry; Zinc sulfides
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201001093

Although quantum dot (QD)‐based room temperature phosphorescence (RTP) probes are promising for practical applications in complex matrixes such as environmental, food and biological samples, current QD‐based‐RTP probes are not only quite limited but also exclusively based on the RTP quenching mechanism. Here we report an ascorbic acid (AA) induced phosphorescence enhancement of sodium tripolyphosphate‐capped Mn‐doped ZnS QDs, and its application for turn‐on RTP detection. The chelating ability allows AA to extract the Mn and Zn from the surface of the QDs and to generate more holes which are subsequently trapped by Mn2+, while the reducing property permits AA to reduce Mn3+ to Mn2+ in the excited state, thereby enhancing the excitation and orange emission of the QDs. The enhanced RTP intensity of the QDs increases linearly with the concentration of AA in the range of 0.05–0.8 μM. Thus, a QD‐based RTP probe for AA is developed. The proposed QD‐based turn‐on RTP probe avoids tedious sample pretreatment, and offers good sensitivity and selectivity for AA in the presence of the main relevant metal ions and other molecules in biological fluids. The limit of detection (3s) of the developed method is 9 nM AA, and the relative standard deviation is 4.8 % for 11 replicate detections of 0.1 μM AA. The developed method is successfully applied to the analysis of real samples of human urine and plasma for AA with quantitative recoveries from 96 to 105 %. Vitamin see: The chelating ability of ascorbic acid (AA) enables the extraction of Mn and Zn from the surface of tripolyphosphate‐capped Mn‐doped ZnS quantum dots (QDs) generating more holes that are subsequently trapped by Mn2+. The reducing property of AA results in the reduction of Mn3+ to Mn2+ in an excited state, thus enhancing the excitation and orange emission of the QDs (see scheme). Such AA‐induced phosphorescence enhancement enables selective detection of AA with a detection limit of 9 nM.