Fernandes Rikitha S, Paul Suvendu, Klikar Milan, Bureš Filip, Dey Nilanjan
Department of Chemistry, Birla Institute of Technology and Science Pilani, Hyderabad Campus, Hyderabad, 500078, India.
Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice, 53210, Czech Republic.
Chempluschem. 2025 Jan;90(1):e202400492. doi: 10.1002/cplu.202400492. Epub 2024 Nov 27.
Owing to the carcinogenicity and environmental risks as well as the wide industrial use of hydrazine, we report herein a colorimetric probe for its ratiometric detection in pure water. The developed probe possesses push-pull architecture with 2-(piperidyn-1-yl) thiophene as the donor, N,N'-dibutylbarbituric as the acceptor, and butadiene as the spacer. In contrast to weak solvatochromic behavior in organic solvents, the probe showed distinct optical photophysical properties in water resulting from the formation of nanoscopic aggregates. The probe underwent pronounced spectral changes upon the addition of hydrazine including an 11.5-fold decrease in absorbance and ~2.4-fold fluorescence quenching. The mechanistic investigation revealed the rapid formation of hydrazone upon the interaction of the probe with hydrazine via retro-Knoevenagel reaction as confirmed experimentally and corroborated with DFT calculations. The induced colorimetric and fluorometric changes were utilized in hydrazine sensing with excellent selectivity over other biologically relevant analytes with a detection limit of 0.76 μM in aqueous media. The practical utility of the probe was assessed in real-life natural water samples, while we have also developed a cost-effective portable kit for the on-site hydrazine detection both in the solution and vapor phases.
由于肼具有致癌性和环境风险，且在工业上广泛使用，我们在此报告一种用于在纯水中对其进行比率检测的比色探针。所开发的探针具有推挽结构，以2-(哌啶-1-基)噻吩作为供体，N,N'-二丁基巴比妥酸作为受体，丁二烯作为间隔基。与在有机溶剂中的弱溶剂化显色行为相反，该探针在水中表现出明显的光学光物理性质，这是由于形成了纳米级聚集体。加入肼后，探针发生了显著的光谱变化，包括吸光度下降11.5倍和约2.4倍的荧光猝灭。机理研究表明，探针与肼通过逆Knoevenagel反应相互作用时迅速形成腙，这已通过实验证实并得到密度泛函理论计算的支持。所诱导的比色和荧光变化被用于肼传感，对其他生物相关分析物具有优异的选择性，在水性介质中的检测限为0.76 μM。在实际天然水样中评估了该探针的实用性，同时我们还开发了一种经济高效的便携式试剂盒，用于在溶液和气相中现场检测肼。
