Shukla Nitin, Singhmar Virjesh, Sayala Juhi, Patra Ashis K
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
Inorg Chem. 2025 Jan 27;64(3):1287-1301. doi: 10.1021/acs.inorgchem.4c03955. Epub 2025 Jan 11.
The nucleotides play multiple fundamental roles that are essential in biochemical enzymatic reactions and signaling pathways. Many diseases are closely associated with their dysregulation. Therefore, reliable and sensitive optical probes to discriminate various nucleotides are essential in biochemistry, drug discovery, and disease diagnosis. Furthermore, developing reliable, easy-to-use optical sensors for extremely toxic organophosphonates/nerve-agents is critical to counter public health threats. Luminescent lanthanide(III) complexes have emerged as promising optical bioprobes owing to intraconfigurational f → f transitions. Herein, we present strategically designed Eu(III) probes: [Eu(THC)(X)]Cl () and [Eu(TBC)(X)]Cl/Br () containing pentadentate terpyridine dicarboxylates: 4'-(3,4,5-trihydroxyphenyl)-[2,2':6',2″-terpyridine]-6,6″-dicarboxylic acid (THC) and 4'-phenyl-[2,2':6',2″-terpyridine]-6,6″-dicarboxylic acid (TBC) and X = solvent. The probe is systematically evaluated for discrimination of various NPs and as a luminescent chemodosimetric probe for diethyl chlorophosphate (DCP) as a G-series nerve agent mimic. The time-delayed luminescence is used for discrimination between various adenine-based NPs under physiological conditions. The probe shows high affinity and selectivity for ADP enabling continuous monitoring of the ADP/ATP ratio in a simulated enzymatic reaction. Additionally, acted as a chemodosimetric probe for DCP. The interaction produces a change in the sensitization pathway, enhancing the Eu(III)-based luminescence with a ppb level of detection of DCP (LOD = 758 ppb). Our innovative approach expands applications of lanthanide luminescence for probing nucleotides and the detection of lethal nerve agents.
核苷酸发挥着多种重要作用，这些作用在生化酶促反应和信号通路中至关重要。许多疾病都与其失调密切相关。因此，用于区分各种核苷酸的可靠且灵敏的光学探针在生物化学、药物发现和疾病诊断中必不可少。此外，开发用于剧毒有机磷酸酯/神经毒剂的可靠、易用的光学传感器对于应对公共卫生威胁至关重要。由于其内部组态f→f跃迁，发光镧系(III)配合物已成为有前景的光学生物探针。在此，我们展示了经过策略设计的铕(III)探针：[Eu(THC)(X)]Cl（ ）和[Eu(TBC)(X)]Cl/Br（ ），它们含有五齿三联吡啶二羧酸酯：4'-(3,4,5-三羟基苯基)-[2,2':6',2″-三联吡啶]-6,6″-二羧酸（THC）和4'-苯基-[2,2':6',2″-三联吡啶]-6,6″-二羧酸（TBC）且X = 溶剂。对 探针进行了系统评估，以区分各种核苷磷酸，并作为用于模拟G系列神经毒剂的磷酸二乙酯（DCP）的发光化学计量探针。利用延时发光在生理条件下区分各种基于腺嘌呤的核苷磷酸。 探针显示出对ADP具有高亲和力和选择性，能够在模拟酶促反应中连续监测ADP/ATP比率。此外， 充当了DCP的化学计量探针。该相互作用使敏化途径发生变化，增强了基于铕(III)的发光，对DCP的检测限达到ppb水平（LOD = 758 ppb）。我们的创新方法扩展了镧系发光在探测核苷酸和检测致命神经毒剂方面的应用。
