Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190, Thailand; Nanomaterials Science, Sensors & Catalysis for Problem-Based Projects, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190, Thailand.
Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Mahidol University, 447 Sri-Ayuthaya Road, Phayathai, Ratchathewi, Bangkok, 10400, Thailand.
Talanta. 2022 May 15;242:123305. doi: 10.1016/j.talanta.2022.123305. Epub 2022 Feb 15.
Cadmium ion (Cd (II)) is a highly toxic heavy metal usually found in natural water. Exposure to Cd (II) can produce serious effects in human organs such as Itai-Itai disease. Therefore, the maximum allowance levels of Cd (II) in drinking water and herbal medicines imposed by the World Health Organization (WHO) are 3 μg L and 300 μg kg, respectively. In this work, nitrogen-doped graphene quantum dots (N-GQDs) as a fluorescent sensor for Cd (II) determination was developed in both solution-based and paper-based systems. N-GQDs were synthesized from citric acid (CA) and ethylenediamine (EDA) via the hydrothermal method. The synthesized N-GQDs emitted intense blue fluorescence with a quantum yield (QY) of up to 80%. The functional groups on the surface of N-GQDs measured by FTIR were carboxyl (COO), hydroxyl (OH), and amine (NH) groups, suggesting that they could be bound to Cd (II) for complexation. The fluorescence intensity of N-GQDs was gradually enhanced with the increase of Cd (II) concentration. This phenomenon was proved to result from the fluorescence enhancement (turn-on) based on the chelation enhanced fluorescence (CHEF) mechanism. Under the optimum conditions in the solution-based and paper-based systems, the limits of detection (LODs) were found to be 1.09 and 0.59 μg L, respectively. Furthermore, the developed sensors showed relatively high selectivity toward Cd (II) over ten other metal cations and six other anions of different charges. The performance of the sensor in real water and herbal medicine samples exhibited no significant difference as compared to the results of the validation method (ICP-OES). Therefore, the developed sensors can be used as fluorescent sensors for Cd (II) determination with high sensitivity, high selectivity, short incubation time (5 min). As such, the paper-based strategy has excellent promising potential for practical analysis of Cd (II) in water and herbal medicine samples with a trace level of Cd (II) concentrations.
镉离子(Cd(II))是一种剧毒重金属,通常存在于天然水中。暴露于 Cd(II)会对人体器官产生严重影响,如痛痛病。因此,世界卫生组织(WHO)对饮用水和草药中 Cd(II)的最大允许水平分别规定为 3μg/L 和 300μg/kg。在这项工作中,氮掺杂石墨烯量子点(N-GQDs)作为一种荧光传感器,用于测定 Cd(II),分别在基于溶液和基于纸张的系统中进行开发。N-GQDs 通过水热法由柠檬酸(CA)和乙二胺(EDA)合成。合成的 N-GQDs 发出强烈的蓝色荧光,量子产率(QY)高达 80%。通过傅里叶变换红外光谱(FTIR)测量的 N-GQDs 表面的官能团为羧基(COO)、羟基(OH)和胺(NH)基团,表明它们可以与 Cd(II)结合形成配合物。随着 Cd(II)浓度的增加,N-GQDs 的荧光强度逐渐增强。这种现象被证明是基于螯合增强荧光(CHEF)机制的荧光增强(开启)的结果。在基于溶液和基于纸张的系统的最佳条件下,发现检测限(LOD)分别为 1.09 和 0.59μg/L。此外,与其他十种金属阳离子和六种带不同电荷的阴离子相比,所开发的传感器对 Cd(II)表现出相对较高的选择性。与验证方法(ICP-OES)的结果相比,该传感器在实际水样和草药样品中的性能没有显著差异。因此,所开发的传感器可作为具有高灵敏度、高选择性、短孵育时间(5 分钟)的 Cd(II)测定的荧光传感器。因此,基于纸张的策略具有在痕量 Cd(II)浓度下实际分析水和草药样品中 Cd(II)的巨大潜力。