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用于铀超灵敏荧光检测的双配体金属有机框架:一种克服浓度限制的原位痕量富集策略。

Dual-Ligand Metal-Organic Framework for Ultrasensitive Fluorescence Detection of Uranium: An In Situ Trace Enrichment Strategy to Overcome Concentration Limitations.

作者信息

Fu Mengtao, Mao Chengkai, Wei Changhong, Wang Chunxiao, Kan Qihui, Dong Shipeng, Mao Liang

机构信息

State Key Laboratory of Water Pollution Control and Green Resource Recycling, School of the Environment, Nanjing University, Nanjing 210023, China.

Shanghai Institute of Applied Radiation, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China.

出版信息

JACS Au. 2025 Aug 1;5(8):4044-4054. doi: 10.1021/jacsau.5c00663. eCollection 2025 Aug 25.

Abstract

The development of trace analysis technology for uranium pollution has become crucial for ecological protection, owing to the extensive utilization of uranium in the nuclear industry. Fluorescence method has been widely used for the detection of uranium in water, but current research still suffers from insufficient sensitivity, sluggish detection speed, and interference from coexisting ions. This is mainly due to the poor selective enrichment ability of the sensors for trace uranium. Herein, a fluorescent metal-organic framework (MOF) named dual-ligand MOF-AO (DMOF-AO) with high uranium affinity was synthesized via a mixed ligand strategy. The incorporated amidoxime groups served as specific recognition sites, achieving a high quenching selectivity against at least 17 interfering ions. The biomimetic flower-like structure coupled with the second ligand intercalation strategy greatly improves the mass transfer rate, enabling the rapid in situ enrichment of uranium even at trace concentrations. This synergistic design and trace uranium enrichment strategy resulted in high detection sensitivity (LOD of 2.72 nmol L) and ultrashort response time (10 s), surpassing most reported fluorescent sensors. Mechanistic investigations elucidated the coordination configuration and revealed the underlying fluorescence quenching mechanism caused by photoinduced electron transfer. The uranium concentrations in the actual water samples from different regions tested by DMOF-AO were consistent with the gold-standard ICP-MS results, validating the practical reliability. This study demonstrates the promoting effect of improving enrichment ability at trace concentrations on detection sensitivity and establishes an efficient, instantaneous, visualization, and reliable strategy for uranium detection using fluorescent MOF.

摘要

由于铀在核工业中的广泛应用,铀污染痕量分析技术的发展对生态保护至关重要。荧光法已广泛用于水中铀的检测,但目前的研究仍存在灵敏度不足、检测速度缓慢以及共存离子干扰等问题。这主要是由于传感器对痕量铀的选择性富集能力较差。在此,通过混合配体策略合成了一种具有高铀亲和力的荧光金属有机框架(MOF),即双配体MOF-AO(DMOF-AO)。引入的偕胺肟基团作为特异性识别位点,对至少17种干扰离子具有高猝灭选择性。仿生花状结构与第二配体插层策略相结合,大大提高了传质速率,即使在痕量浓度下也能实现铀的快速原位富集。这种协同设计和痕量铀富集策略导致了高检测灵敏度(检测限为2.72 nmol/L)和超短响应时间(10 s),超过了大多数已报道的荧光传感器。机理研究阐明了配位构型,并揭示了光致电子转移引起的潜在荧光猝灭机制。用DMOF-AO测试的不同地区实际水样中的铀浓度与金标准ICP-MS结果一致,验证了实际可靠性。本研究证明了提高痕量浓度下的富集能力对检测灵敏度的促进作用,并建立了一种使用荧光MOF进行铀检测的高效、即时、可视化和可靠的策略。

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