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分子受体集成了双峰多孔聚合物支架,作为便携式固态光学离子传感器和萃取器,用于选择性捕获超痕量有毒铜离子。

Molecular receptors integrated bimodal porous polymer scaffolds as portable solid-state optical ion-sensors and extractors for the selective capturing of ultra-trace toxic copper ions.

作者信息

Pavoor Veedu Anju, Mohan Akhila Maheswari, Jeyakumar Balasurendran, Roy Jismi, Srinivasan Prabhakaran, Nagarajan Sivaraman, Deivasigamani Prabhakaran

机构信息

Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology (VIT), Vellore, Tamil Nadu, 632014, India.

Homi Bhabha National Institute, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu, 603102, India.

出版信息

Anal Chim Acta. 2024 Jun 8;1307:342625. doi: 10.1016/j.aca.2024.342625. Epub 2024 Apr 20.

DOI:10.1016/j.aca.2024.342625
PMID:38719404
Abstract

BACKGROUND

Environmental contamination by heavy metal ions has caused growing ecological and public health concerns. In this line, monitoring of copper toxicity gains importance due to its application in industrial, agricultural, domestic, medical and technological sectors. Although noteworthy breakthroughs were made, critical issues, such as portability, the need for well-trained personnel, costly/complex instrumentations, long response time, and the introduction of secondary contaminants, required attention. Hence, developing a low-cost, user-friendly, real-time, portable analytical platform for rapid and on-site analysis remained imperative. Solid-state colorimetric sensors have gained widespread popularity due to their low cost, ease of use, and brilliant sensitivity/selectivity.

RESULTS

We have successfully unfolded an ultra-portable azomethine-infused structurally interwoven polymer monolith as the solid-state chromatic sensor for the quantitative naked-eye detection of ultra-trace Cu in industrial/environmental samples. For the sensor fabrication, non-hygroscopic conjugated Schiff-base receptors, namely N-(1E,2E)-3-(4-dimethylamino)phenyl)allylidene)-3-nitrobenzohydrazide (DPAN) and 2,3-bis(((1E,2E)-3-(4-dimethylamino)phenyl)allylidene)amino)malononitrile (DPAM) were synthesized in-house and voluminously immobilized onto a crack-free porous poly(4VP-co-EGDMA) monolith framework. The topological structure and functionalities of the porous polymer monolith and chromatic sensor materials were examined using various surface analytical and microscopic techniques. The excellent surface area and intriguing interlaced porosity features of the tailor-made polymer monolith facilitated the voluminous anchoring of the chromatic receptors for the selective/sensitive targeting of Cu. The DPAN and DPAM receptor-loaded poly(4VP-co-EGDMA) sensors exhibited a linear range of 0-150 μg/L, with the limit of detection of 0.11 and 0.13 μg/L for Cu, respectively. The sensors manifested Cu specificity amidst concomitant matrix ions to highlight the relevance of the proposed solid-state sensor.

SIGNIFICANCE

The sensor materials offered a reliable approach for detecting and quantifying environmentally toxic and industrially pertinent Cu from aqueous samples, with the prospect of large-scale production, owing to the sensor's integrated compact design that can be reused for repeated real-time surveillance. The sensor's ability to sense/trap traces of toxic Cu can provide an early warning about the growing toxicity in a particular resource, thereby providing an opportunity to initiate remediation protocols for speedy decontamination.

摘要

背景

重金属离子对环境的污染已引发越来越多的生态和公共卫生问题。据此,由于铜在工业、农业、家庭、医疗和技术领域的应用,对其毒性的监测变得愈发重要。尽管已取得显著突破,但诸如便携性、需要训练有素的人员、仪器成本高/复杂、响应时间长以及引入二次污染物等关键问题仍需关注。因此,开发一种低成本、用户友好、实时、便携式的分析平台以进行快速现场分析仍然势在必行。固态比色传感器因其低成本、易于使用以及出色的灵敏度/选择性而广受欢迎。

结果

我们成功展示了一种超便携式的注入偶氮甲碱的结构交织聚合物整体材料,作为用于工业/环境样品中超痕量铜定量肉眼检测的固态比色传感器。对于传感器的制备,在内部合成了非吸湿共轭席夫碱受体,即N-(1E,2E)-3-(4-二甲基氨基苯基)亚烯丙基)-3-硝基苯甲酰肼(DPAN)和2,3-双(((1E,2E)-3-(4-二甲基氨基苯基)亚烯丙基)氨基)丙二腈(DPAM),并大量固定在无裂纹的多孔聚(4VP-co-EGDMA)整体框架上。使用各种表面分析和显微镜技术研究了多孔聚合物整体材料和比色传感器材料的拓扑结构和功能。定制的聚合物整体材料优异的表面积和有趣的交错孔隙特征促进了比色受体的大量锚定,以实现对铜的选择性/灵敏靶向。负载DPAN和DPAM受体的聚(4VP-co-EGDMA)传感器的线性范围为0-150μg/L,铜的检测限分别为0.11和0.13μg/L。该传感器在伴随的基质离子中表现出对铜的特异性,突出了所提出的固态传感器的相关性。

意义

传感器材料为从水样中检测和定量环境有毒和工业相关的铜提供了一种可靠方法,由于传感器集成紧凑的设计可重复用于实时监测,具有大规模生产的前景。该传感器检测/捕获痕量有毒铜的能力可为特定资源中不断增加的毒性提供早期预警,从而为启动快速净化的修复方案提供机会。

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