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用于通过形成氰基双硫腙加合物灵敏检测水中氰化物的小型化双波长β校正分光光度探头。

Miniaturized dual-wavelength β-correction spectrophotometric probe for sensitive detection of cyanide in water via formation of cyano dithizone adduct.

作者信息

Bahaidarah E A, Alwael H, Dabi M M, Abduljabbar T N, Alshareef F M, Alzahrani K A, Asiri N A, Maslamani N O, Bahaffi S O, El-Shahawi M S

机构信息

Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia.

Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia; Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, Jeddah 21589, Saudi Arabia.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2025 Feb 15;327:125314. doi: 10.1016/j.saa.2024.125314. Epub 2024 Oct 20.

Abstract

Cyanide toxicity in water significantly threatens public health and the environment. To address this, a miniaturized simple, low-cost, selective and sensitive direct dual wave β-correction spectrophotometric probe has been established for cyanide detection in water. The dual-wavelength β-correction spectrophotometry enhances the selectivity and sensitivity of the probe in the presence of interfering species. The assay relies a highly selective nucleophilic addition of cyanide ions to dithizone (HDz) as chromogenic reagent in aqueous media of pH 6.8-7.2, forming a red-colored cyano HDz adduct. The electronic spectrum of the formed adduct displays a sharp absorption peak at λ = 480 nm, enabling precise colorimetric detection. The molar absorptivity and Sandell's sensitivity index for the cyano HDz adduct with and without β-correction spectrophotometry were 5.62 × 10, and 1.79 × 10 L mol cm, and 0.002 and 0.0033 µg cm, respectively. Beer's law and Ringbom's plots are valid in the range 0.01-5.0 and 0.06-2.0 µg mL CN concentration, respectively. The limits of detection (LOD) and quantification (LOQ) improved from 1.03 × 10 and 3.13 × 10 μg/mL using ordinary spectrophotometry to 2.8 × 10 and 8.7 × 10 μg mL employing β-correction spectrophotometry. The probe offers rapid response, good anti-interference ability, reproducibility, and cost-effectiveness. The probe was successfully applied for detection of trace levels of cyanide ions in water with good repeatability. It has been also validated in water samples with good recoveries (99.2 ± 5.02 %). The experimental Student t test (t = 1.2-1.5) was lower than the critical (t = 2.78) at 95 % probability (n = 5). The stoichiometry and mechanism of formation of the cyano adduct were assigned and addressed.

摘要

水中的氰化物毒性对公众健康和环境构成重大威胁。为解决这一问题,已建立了一种小型化、简单、低成本、选择性和灵敏的直接双波长β校正分光光度法探针,用于检测水中的氰化物。双波长β校正分光光度法在存在干扰物质的情况下提高了探针的选择性和灵敏度。该测定法依赖于在pH 6.8 - 7.2的水性介质中,氰离子与作为显色剂的双硫腙(HDz)进行高度选择性的亲核加成,形成红色的氰基HDz加合物。所形成加合物的电子光谱在λ = 480 nm处显示出一个尖锐的吸收峰,从而能够进行精确的比色检测。采用和不采用β校正分光光度法时,氰基HDz加合物的摩尔吸光系数和桑德尔灵敏度指数分别为5.62×10和1.79×10 L·mol⁻¹·cm⁻¹,以及0.002和0.0033 μg·cm⁻²。比尔定律和林邦曲线分别在CN⁻浓度为0.01 - 5.0和0.06 - 2.0 μg/mL的范围内有效。检测限(LOD)和定量限(LOQ)从使用普通分光光度法时的1.03×10和3.13×10 μg/mL提高到采用β校正分光光度法时的2.8×10和8.7×10 μg/mL。该探针具有响应迅速、抗干扰能力强、重现性好且成本效益高的特点。该探针已成功应用于水中痕量氰离子的检测,具有良好的重复性。它在水样中也得到了验证,回收率良好(99.2±5.02%)。实验学生t检验(t = 1.2 - 1.5)低于95%概率下的临界值(t = 2.78)(n = 5)。对氰基加合物的化学计量和形成机理进行了确定和探讨。

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