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An efficient ratiometric fluorescence sensor based on metal-organic framework and quantum dots for highly selective detection of 6-mercaptopurine
Summary:
The authors from Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province; Key Laboratory of Medicinal Resource and Natural Pharmaceutical Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal University developed a ratiometric fluorescence sensor based on NH₂-MIL-53(Al) and MPA-CdTe QDs with high selectivity and sensitivity, achieving good results in the detection of 6-mercaptopurine (6-MP) in human urine samples.
Background:
1. To address the problem of detecting 6-MP accurately and efficiently, previous researchers conducted work using methods such as capillary electrophoresis, electrochemical methods, chemiluminescence, HPLC, MS, and fluorescence methods, achieving certain success, yet there are problems like poor selectivity, low sensitivity, expensive equipment, and complicated sample pretreatments.
2. The authors in this study proposed an innovative method of developing a ratiometric fluorescence sensor by combining NH₂-MIL-53(Al) and MPA-CdTe QDs, obtaining a detection limit of 0.15 μM for 6-MP with high selectivity and good stability.
Research Content:
1. Synthesis:
The authors synthesized NH₂-MIL-53(Al) using a hydrothermal method by dissolving AlCl₃·6H₂O and NH₂-BDC in deionized water, reacting in an autoclave at 150 °C for 5 h, and subsequent treatment. MPA-CdTe QDs were synthesized using a one-pot method by dissolving CdCl₂·2.5H₂O, adding MPA, trisodium citrate dihydrate, Na₂TeO₃, and NaBH₄, adjusting pH, and refluxing.
2. Characterizations:
1) No BET and pore size distribution results are mentioned.
2) SEM/TEM tests show that NH₂-MIL-53(Al) has a regular rhomboid structure with a particle size of around 1 μm, and MPA-CdTe QDs are nearly spherical with a diameter of ~3 nm.
3) Other tests: FTIR spectra of NH₂-MIL-53(Al) show bands related to NH₂ group and carbonyl groups; XRD patterns confirm the pure phase of NH₂-MIL-53(Al); UV/Vis absorption spectrum of MPA-CdTe QDs reveals an absorption band at ~500 nm; fluorescence spectra show NH₂-MIL-53(Al) emits at 425 nm and MPA-CdTe QDs emit at 528 nm under excitation at 335 nm.
3. Application:
The material was tested in the detection of 6-MP, with a linear range of 0–50 μM and a detection limit of 0.15 μM. It was also applied to detect 6-MP in human urine samples, with recoveries of 102.4–104.6% and RSDs of 2.9–4.4%.
4. Mechanism:
The fluorescence of NH₂-MIL-53(Al) is quenched by 6-MP due to strong inner filter effects (IFEs) caused by spectral overlap. The fluorescence of MPA-CdTe QDs is enhanced because the thiol group of 6-MP binds to Cd²⁺ surface traps on QDs, removing trap states and improving photoluminescence.
Outlook:
This research successfully developed a novel ratiometric fluorescence sensor for 6-MP detection, which has high selectivity, sensitivity, and stability, and shows potential in real sample analysis, contributing to the field of chemical material-based sensing.
An efficient ratiometric fluorescence sensor based on metal-organic framework and quantum dots for highly selective detection of 6-mercaptopurine
Authors: Meng Jin, Zhao-Li Mou, Rui-Ling Zhang, Si-Si Liang, and Zhi-Qi Zhang
DOI: 10.1016/j.bios.2016.12.022
Link: https://www.sciencedirect.com/science/article/pii/S0956566316312490
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