Determination of Hg2+ in Water with Rhodamine 6G Derivative-Glutothione as Fluorescent Probe
摘 要
在罗丹明6G衍生物(Rh6G2)中引入谷胱甘肽(GSH),制备了一种荧光探针Rh6G2-GSH,并基于其与Hg2+识别时可发生荧光强度及吸光度的变化,分别采用荧光分光光度法和紫外-可见分光光度法测定水中Hg2+的含量。在由体积比为1:1的4-羟乙基哌嗪乙磺酸(HEPES)溶液和甲醇混合而成的缓冲溶液(pH 7)中加入Rh6G2和GSH,通过自组装反应合成荧光探针Rh6G2-GSH,将其加入到水样中,分别在优化的两种方法的仪器工作条件下测定。结果显示:荧光探针可在较宽的酸度范围内(pH 7~12)识别Hg2+,且受常见金属阳离子干扰小;两种方法制作的标准曲线的线性范围分别为2.5×10-5~2.5×10-4mol·L-1和5.0×10-5~2.5×10-4mol·L-1,检出限分别为1.39×10-9mol·L-1和4.07×10-7mol·L-1;对实际样品进行3个浓度水平的加标回收试验,两种方法所得的回收率分别为95.1%~120%和94.8%~100%,测定值的相对标准偏差(n=5)分别为0.46%~2.4%和0.15%~3.4%。采用四极杆-飞行时间质谱仪对荧光检测机理进行探究,发现Rh6G2-GSH在与Hg2+进行不可逆的结合后,会进一步发生水解,生成一种荧光强度更高的有机酸。
Abstract
Glutathione (GSH) was introduced into rhodamine 6G derivative (Rh6G2) to prepare a fluorescent probe Rh6G2-GSH, and Hg2+ content in water was determined by fluorescence spectroscopy and ultraviolet-visible spectrophotometry based on the changes in fluorescence intensity and absorbance occurred in the process of the fluorescent probe for recognition of Hg2+. Rh6G2 and GSH were added into a buffer solution (pH 7.0) composed of HEPES solution and methane with volume ratio of 1:1, and the fluorescent probe of Rh6G2-GSH was synthesized by self-assembly reaction. The fluorescent probe was mixed with the water sample, and the mixed solution was measured under the optimized instrument working conditions of the two methods. The results showed that the fluorescent probe could recognize Hg2+ in a wide acidity range (pH 7-12), with a less interference produced by common metal cations; linearity ranges of the standard curves made by the two methods were found in the ranges of 2.5×10-5-2.5×10-4 mol·L-1 and 5.0×10-5-2.5×10-4 mol·L-1, with detection limits of 1.39×10-9 mol·L-1 and 4.07×10-7 mol·L-1. The recovery test was made on the actual samples by standard addition method at three concentration levels, giving recoveries in the ranges of 95.1%-120% and 94.8%-100%, and RSDs of determined values (n=5) were found in the ranges of 0.46%-2.4% and 0.15%-3.4%. Quadrupole-time-of-flight mass spectrometer was used to investigate the fluorescence detection mechanism, and it turned out that after Rh6G2-GSH was irreversibly combined with Hg2+, it would undergo further hydrolysis to give an organic acid with a higher fluorescence intensity.
中图分类号 O655 DOI 10.11973/lhjy-hx202105001
所属栏目 试验与研究
基金项目 国家自然科学基金(21665027);国家大学生创新创业训练计划项目(201710691004);云南省教育厅科学研究基金项目(2020J0327)
收稿日期 2020/4/9
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联系人作者谭伟(317366182@qq.com)
备注赵秋媛,硕士研究生,研究方向为荧光探针制备及重金属离子检测
引用该论文: ZHAO Qiuyuan,YANG Jianhua,WANG Rui,ZHANG Lizhu,YANG Min,ZHANG Yanli,WANG Hongbin,TAN Wei. Determination of Hg2+ in Water with Rhodamine 6G Derivative-Glutothione as Fluorescent Probe[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2021, 57(5): 385~390
赵秋媛,杨剑华,王蕊,张丽珠,杨敏,张艳丽,王红斌,谭伟. 罗丹明6G衍生物-谷胱甘肽荧光探针测定水中Hg2+[J]. 理化检验-化学分册, 2021, 57(5): 385~390
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【4】田韫琪,周鹏飞,苏伟,等.罗丹明6G酰肼Hg2+荧光探针及细胞成像应用[J].化学研究与应用, 2017,29(4):551-554.
【5】刘大海,张雪妍,冯玉沙,等.基于荧光素硫代酰肼类Hg2+荧光探针的合成及在生物成像中的应用[J].高等学校化学学报, 2018,39(7):1412-1419.
【6】韩文强,田茂忠,冯锋.一种基于罗丹明类染料的汞(Ⅱ)荧光探针的研究[J].分析试验室, 2017,36(3):273-276.
【7】杜方凯,李梦汝,莫远健,等.基于聚多巴胺纳米粒子的荧光增强型探针检测乙酰胆碱酶[J].分析测试学报, 2019,38(11):1347-1352.
【8】袁跃华,冯锋,田茂忠,等.罗丹明类荧光探针的合成及对铜离子的检测[J].高等学校化学学报, 2011,32(1):62-66.
【9】ZHAO M L, YANG X F, HE S F, et al. A rhodamine-based Hg2+-selective fluorescent probe in aqueous solution[J]. Chemical Papers, 2009,63(3):261-267.
【10】YU C W, ZHANG J, WANG R, et al. Highly sensitive and selective colorimetric and off-on fluorescent probe for Cu2+ based on rhodamine derivative[J]. Organic & Biomolecular Chemistry, 2010,8(23):5277-5279.
【11】TANG B, XING Y L, LI P, et al. A rhodamine-based fluorescent probe containing a Se-N bond for detecting thiols and its application in living cells[J]. Journal of the American Chemical Society, 2007,129(38):11666-11667.
【12】周丽波,赵秋媛,李宜,等.基于高半胱氨酸-罗丹明类荧光探针的合成及其对水中铜离子的检测[J].分析试验室, 2018,37(8):893-897.
【13】CHAI F, WANG C G, WANG T T, et al. Colorimetric detection of Pb2+ using glutathione functionalized gold nanoparticles[J]. ACS Applied Materials & Interfaces, 2010,2(5):1466-1470.
【14】刘云龙.罗丹明荧光探针的设计、合成及光谱研究[D].太原:山西大学, 2012.
【15】康人桂,李在久.环境监测分析中的零浓度、检出限与测定下限[J].环境科学丛刊, 1985(12):15-21.
【16】董哲,李阳,郑庆福,等.新型荧光探针制备及茶叶中汞离子检测的研究[J].中国酿造, 2019,38(8):178-182.
【17】廖贤,袁剑英,牟兰,等.纯水中检测汞离子与银离子的菲啰啉类荧光探针[J].分析测试学报, 2019,38(6):706-711.
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