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镧系金属-有机框架免修饰荧光各向异性探针检测磷酸根离子OA北大核心CSTPCD

Lanthanide Metal Organic Framework as A New Unlabeled Fluorescence Anisotropy Probe for Detection of Phosphate Ions

中文摘要英文摘要

荧光各向异性(FA)分析法具有免分离、高通量和实时检测等优势,广泛应用于诸多领域.然而,当分析物的体积或质量较小时,与荧光探针结合后不能产生明显的信号变化,导致灵敏度较低.为解决此问题,研究者通常采用纳米材料增强发光体的质量或体积的方式放大FA来提升检测灵敏度.然而,这些方法也存在纳米材料易猝灭荧光而降低准确度以及荧光探针修饰步骤复杂等弊端,因此,有必要开发不需要放大体积和质量且免修饰的新型FA探针.发光金属-有机框架作为一种新兴的发光纳米材料,由于其自身具有较大的体积和质量以及较高的FA值(r),无需额外的信号放大,是作为FA探针的理想材料.本研究通过微波辅助法成功合成了以铈离子(Ce3+)为中心离子、5,10,15,20-四(4-羧基苯基)卟啉(H2TCPP)为配体的镧系金属-有机框架(Ce-TCPP MOF),并将其作为一种新型的免修饰FA探针用于检测磷酸根离子(Pi).未加入Pi时,Ce-TCPP MOF具有较大的r;加入Pi后,MOF中的Ce3+与Pi发生反应,破坏了MOF的结构,产生质量或体积更小的碎片,使r降低.随着Pi浓度增加,Ce-TCPP MOF的r的降低值(Δr)逐步增大,Δr与Pi浓度在0.5~3.5 μmol/L(0.016~0.108 mg/L)范围内呈良好的线性关系,检出限(LOD,3σ/k)为0.41 μmol/L.采用本方法测得嘉陵江水中Pi浓度约为0.078 mg/L,采用钼酸铵分光光度法测得Pi浓度约为0.080 mg/L,二者检测结果一致,表明本方法可用于复杂水体中Pi的检测.

Fluorescence anisotropy(FA)analysis has many advantages such as no requirement of separation,high throughput and real-time detection,and thus has been widely used in many fields,including biochemical analysis,food safety detection,environmental monitoring,etc.However,due to the small volume or mass of the target,its combination with the fluorescence probe cannot produce significant signal change.To solve this issue,researchers often use nanomaterials to enhance the mass or volume of fluorophore to improve the sensitivity.Nevertheless,this FA amplification strategy also has some disadvantages.Firstly,nanomaterials are easy to quench fluorescence.As a result,the FA value is easily influenced by light scattering,which reduces the detection accuracy.Secondly,fluorescent probes in most methods require complex modification steps.Therefore,it is necessary to develop new FA probes that do not require the amplification of volume and mass or modification.As a new kind of nanomaterials,luminescent metal-organic framework(MOF)has a large volume(or mass)and strong fluorescence emission.It does not require additional signal amplification materials.As a consequence,it can be used as a potential FA probe.This study successfully synthesized a lanthanide metal organic framework(Ce-TCPP MOF)using cerium ion(Ce3+)as the central ion and 5,10,15,20-tetra(4-carboxylphenyl)porphyrin(H2TCPP)as the ligand through microwave assisted method,and used it as a novel unmodified FA probe to detect phosphate ions(Pi).In the absence of Pi,Ce-TCPP MOF had a significant FA value(r).After addition of Pi,Pi reacted with Ce3+in MOF and destroyed the structure of MOF into the small pieces,resulting in a decrease in r.The experimental results indicated that with the increase of Pi concentration,the change of the r of Ce-TCPP MOF(Δr)gradually increased.The Δr and Pi concentration showed a good linear relationship within the range of 0.5-3.5 μmol/L(0.016-0.108 mg/L).The limit of detection(LOD,3σ/k)was 0.41 μmol/L.The concentration of Pi in the Jialing River water detected by this method was about 0.078 mg/L,and the Pi value detected by ammonium molybdate spectrophotometry was about 0.080 mg/L.The two detection results were consistent with each other,and the detection results also meet the ClassⅡwater quality standard,proving that this method could be used for the detection of Pi in complex water bodies.

毛凯;王小燕;罗玉洁;谢佳丽;谢添锦;李原芳;黄承志;甄淑君

西南大学化学化工学院,重庆 400715西南大学药学院,重庆 400715

荧光各向异性探针发光金属-有机框架镧系金属-有机框架磷酸根离子

Fluorescence anisotropyProbesLuminescent metal organic frameworkLanthanide metal organic frameworkPhosphate ions

《分析化学》 2024 (001)

DNA纳米结构增强发光纳米颗粒荧光各向异性的机理及分析应用研究

35-44,中插1-中插4 / 14

国家自然科学基金项目(No.21974109)和重庆市自然科学基金项目(No.CSTB2022NSCQ-MSX1662)资助. Supported by the National Natural Science Foundation of China(No.21974109)and the Natural Science Foundation of Chongqing,China(No.CSTB2022NSCQ-MSX1662).

10.19756/j.issn.0253-3820.231348

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