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一种基于丹磺酰修饰肽的新型铀酰离子荧光传感器。

A novel fluorescence sensor for uranyl ion detection based on a dansyl-modified peptide.

作者信息

Zhang Lianshun, Jia Mengqing, Wang Xi, Gao Lei, Zhang Bo, Wang Lei, Kong Jinming, Li Lianzhi

机构信息

School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, PR China.

Zhong Yuan Academy of Biological Medicine, Liaocheng People's Hospital, Liaocheng 252000, PR China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2023 May 5;292:122403. doi: 10.1016/j.saa.2023.122403. Epub 2023 Jan 25.

Abstract

It is of great significance to sensitively and selectively detect uranyl ion (UO) in environmental and biological samples due to the high risks of UO to human health. However, such suitable sensors are still scarce. A novel fluorescence sensor based on a dansyl-modified peptide, Dansyl-Glu-Glu-Pro-Glu-Trp-COOH (D-P5), was efficiently synthesized by Fmoc solid phase peptide synthesis. As the first linear peptide-based fluorescence sensor for UO, D-P5 exhibited high selectivity and sensitivity to UO over 27 metal ions (UO, Cr, Cu, Ba, Hg, Pb, Co, Ag, Fe, Ca, K, Mg, Mn, Na, Ni, Cd, Zn, Al, Dy, Er, Gd, Ho, La, Lu, Pr, Sm, Tm) by a turn-off fluorescence response in 10 mM HEPES buffer (pH 6.3). The effects of anions such as S, NO, SO CO, HCOO, antioxidant ascorbic acid and 4-nitrophenyl acetate on the selectivity for UO detection were also studies. D-P5 sensor could be used for detecting UO in a good linear relationship with concentration in the range of 0-8.0 μM with a low limit of detection of 83.2 nM. Furthermore, the interaction of the sensor with UO was characterized by ESI-MS, IR, XPS and ITC measurements. The 1:1 binding stoichiometry between the sensor and UO was measured by the job's plot and further verified by ESI-MS. The binding constant of the sensor with UO was calculated to be 9.8 × 10 M by modified Benesi-Hildebrand equation. ITC results showed that theΔH andΔS for the interaction of D-P5 with UO were -(7.167 ± 1.25) kJ·mol and 66.5 J·mol·K, respectively. Time-resolved fluorescence spectroscopy indicated that the mechanism of fluorescence quenching of D-P5 by UO ion was static quenching process. In addition, this sensor displayed a good practicality for UO detection in lake water sample without tedious sample pretreatment.

摘要

由于铀酰离子(UO)对人类健康具有高风险,因此灵敏且选择性地检测环境和生物样品中的铀酰离子具有重要意义。然而,此类合适的传感器仍然稀缺。通过芴甲氧羰基(Fmoc)固相肽合成法高效合成了一种基于丹磺酰修饰肽Dansyl-Glu-Glu-Pro-Glu-Trp-COOH(D-P5)的新型荧光传感器。作为首个基于线性肽的铀酰离子荧光传感器,D-P5在10 mM 4-(2-羟乙基)-1-哌嗪乙磺酸(HEPES)缓冲液(pH 6.3)中通过荧光猝灭响应,对铀酰离子表现出高于27种金属离子(UO、Cr、Cu、Ba、Hg、Pb、Co、Ag、Fe、Ca、K、Mg、Mn、Na、Ni、Cd、Zn、Al、Dy、Er、Gd、Ho、La、Lu、Pr、Sm、Tm)的高选择性和灵敏度。还研究了诸如S、NO、SO、CO、HCOO等阴离子、抗氧化剂抗坏血酸和4-硝基苯乙酸对铀酰离子检测选择性的影响。D-P5传感器可用于检测铀酰离子,在0 - 8.0 μM浓度范围内与浓度呈良好的线性关系,检测下限低至83.2 nM。此外,通过电喷雾电离质谱(ESI-MS)、红外光谱(IR)、X射线光电子能谱(XPS)和等温滴定量热法(ITC)测量对传感器与铀酰离子的相互作用进行了表征。通过工作曲线法测得传感器与铀酰离子的结合化学计量比为1:1,并通过ESI-MS进一步验证。通过修正的贝内西-希尔德布兰德方程计算出传感器与铀酰离子的结合常数为9.8×10 M。ITC结果表明,D-P5与铀酰离子相互作用的焓变(ΔH)和熵变(ΔS)分别为-(7.167±1.25) kJ·mol和66.5 J·mol·K。时间分辨荧光光谱表明,铀酰离子对D-P5的荧光猝灭机制为静态猝灭过程。此外,该传感器在无需繁琐样品预处理的情况下,对湖水样品中的铀酰离子检测显示出良好的实用性。

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