PDF(Pubmed)
Abstract：
Estrone (E1), as an endogenous estrogen, has a variety of physiological functions in human body and is of great significance to human health. On the other hand, it is a widely distributed and highly disturbing environmental endocrine disruptor in water. Therefore, there is an urgent need to develop a sensitive, rapid, and inexpensive method for the on-site determination of E1, which is not only for clinical diagnosis and treatment, but also for the investigation and monitoring of endogenous estrogen pollution in environmental water. In this study, Ru(bpy)3 2+/MWCNTs/Nafion/gold electrodes were prepared by surface electrostatic adsorption and ion exchange. A molecularly imprinted membrane (MIP) with the capability to recognize E1 molecules was prepared by sol-gel method, and the electrodes were modified with MIP to form an electrochemical luminescence sensor (MIP-ECL). This method simultaneously possesses ECL\'s advantage of high sensitivity and MIP\'s advantage of high selectivity. Moreover, the addition of carboxylated multi-walled carbon nanotubes (MWCNT-COOH) improved the functionalization of the gold electrode surface and increased the binding sites of MIP. Meanwhile, the good conductivity of MWCNTs promoted electron transfer and further improved the sensitivity of the sensor. The sensor showed a wide linear interval in which the E1 concentrations can range from 0.1 μg/L to 200 μg/L, along with a high linear correlation coefficient (R 2 = 0.999). The linear regression equation of the sensor was Y = 243.64x-79.989, and the detection limit (LOD) was 0.0047 μg/L. To validate our sensor, actual samples were also measured by the reference method (LC-MS/MS), and it was found that the relative deviation of quantitative results of the two different methods was less than 4.1%. This indicates that the quantitative results obtained by this sensor are accurate and can be used for rapid in situ determination of E1 in clinical samples and environmental water.
摘要：
Estrone(E1),作为内源性雌激素，人体具有多种生理功能,对人体健康具有重要意义。另一方面,它是一种广泛分布和高度令人不安的环境内分泌干扰物。因此,迫切需要发展一种敏感的，快速,和便宜的方法，用于现场确定E1，这不仅是临床诊断和治疗，还用于环境水中内源性雌激素污染的调查和监测。在这项研究中,通过表面静电吸附和离子交换制备了Ru(bpy)32+/MWCNTs/Nafion/金电极。通过溶胶-凝胶法制备了具有识别E1分子能力的分子印迹膜（MIP），并用MIP修饰电极以形成电化学发光传感器(MIP-ECL)。该方法同时具有ECL的高灵敏度优势和MIP的高选择性优势。此外，羧化多壁碳纳米管（MWCNT-COOH）的加入改善了金电极表面的功能化并增加了MIP的结合位点。同时,MWCNTs良好的导电性促进了电子转移,进一步提高了传感器的灵敏度。传感器显示了一个宽的线性区间，其中E1浓度范围从0.1μg/L到200μg/L，具有较高的线性相关系数(R2=0.999)。传感器的线性回归方程为Y=243.64x-79.989，检出限（LOD）为0.0047μg/L。为了验证我们的传感器，实际样品也通过参考方法(LC-MS/MS)测量，两种方法定量结果的相对偏差均小于4.1%。这表明该传感器获得的定量结果准确，可用于临床样品和环境水中E1的快速原位测定。
