Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry (Tianjin Normal University), Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, College of Chemistry, Tianjin Normal University, 393 Binshui West Road, Tianjin 300387, PR China.
Dalton Trans. 2019 Nov 21;48(43):16199-16210. doi: 10.1039/c9dt02971k. Epub 2019 Sep 18.
Alkaline phosphatase (ALP), an extraordinary enzyme, can catalyze the dephosphorylation of small molecules, proteins and nucleic acids. ALP has been confirmed as a crucial serum diagnostic indicator, since the abnormal level of ALP is closely related to a variety of pathological processes, especially in the early diagnosis and screening of cancer. Herein, we designed a "turn-on" sensor to detect ALP and ascorbic acid (AA) based on the redox reaction between manganese dioxide (MnO) coated upconversion nanoparticles (UCNPs) and AA. Firstly, 2 nm sized NaYF:Yb,Tm UCNPs were synthesized by a facile one-pot hydrothermal method. Then MnO coated UCNPs were prepared via electrostatic interactions between MnO nanosheets and UCNPs. MnO nanosheets could absorb blue light emitted by UCNPs near 471 nm under laser excitation at 980 nm, and so the luminescence of UCNPs was quenched based on luminescence energy transfer (LET). In the presence of AA, the luminescence was recovered again by the redox reaction between AA and MnO coated UCNPs. MnO nanosheets were reduced to Mn and UCNPs were released. Furthermore, the "turn-on" sensor was applied to monitor ALP since the phosphate group of 2-phospho-l-ascorbic acid (AAP) was removed by ALP to yield AA. The bio-assay showed a good linear relationship between the restored luminescence intensities (ΔI = I-I) and ALP concentrations ranging from 0.25 to 150 mU mL with a limit of detection (LOD) of 0.045 mU mL and between ΔI and AA concentrations ranging from 0.5 to 250 μM with an LOD of 0.29 μM. The luminescent sensor was also successfully applied for detection of ALP and AA in human serum samples with recoveries from 94.9% to 104.6% and 99.4% to 104.9%.
碱性磷酸酶 (ALP) 是一种特殊的酶,能够催化小分子、蛋白质和核酸的去磷酸化。ALP 已被证实是一种重要的血清诊断指标,因为 ALP 的异常水平与多种病理过程密切相关,特别是在癌症的早期诊断和筛查中。在这里,我们设计了一种基于二氧化锰 (MnO) 涂层上转换纳米粒子 (UCNPs) 与 AA 之间的氧化还原反应来检测 ALP 和抗坏血酸 (AA) 的“开启”传感器。首先,通过简便的一锅水热法合成了 2nm 大小的 NaYF:Yb,Tm UCNPs。然后通过 MnO 纳米片与 UCNPs 之间的静电相互作用制备了 MnO 涂层 UCNPs。在 980nm 激光激发下,MnO 纳米片可以吸收 UCNPs 在 471nm 附近发出的蓝光,因此基于荧光能量转移 (LET),UCNPs 的荧光被猝灭。在 AA 的存在下,AA 和 MnO 涂层 UCNPs 之间的氧化还原反应使荧光恢复。MnO 纳米片被还原为 Mn,UCNPs 被释放。此外,由于 ALP 去除 2-磷酸-L-抗坏血酸 (AAP) 的磷酸基团生成 AA,因此该“开启”传感器可用于监测 ALP。生物测定显示,恢复的荧光强度 (ΔI=I-I) 与 ALP 浓度在 0.25 至 150mU mL 之间呈良好的线性关系,检测限 (LOD) 为 0.045mU mL,ΔI 与 AA 浓度在 0.5 至 250μM 之间呈线性关系,LOD 为 0.29μM。该发光传感器还成功地应用于人血清样品中 ALP 和 AA 的检测,回收率为 94.9%至 104.6%和 99.4%至 104.9%。