Oh Jeong-Wook, Yoon Yeo Woon, Heo Jihye, Yu Joonhee, Kim Hasuck, Kim Tae Hyun
Department of Chemistry, Seoul National University, Seoul 08826, Republic of Korea.
Department of Chemistry, Soonchunhyang University, Asan 31538, Republic of Korea.
Talanta. 2016 Jan 15;147:453-9. doi: 10.1016/j.talanta.2015.10.020. Epub 2015 Oct 8.
Negatively charged multi-walled carbon nanotubes (MWCNTs) were prepared using simple sonication technique with non-toxic citric acid (CA) for the electrochemical detection of dopamine (DA). CA/MWCNTs were placed on glassy carbon (GC) electrodes by drop-casting method and then electrochemical determinations of DA were performed in the presence of highly concentrated ascorbic acid (AA). For the comparison of the charge effect on MWCNTs surface, positively charged polyethyleneimine (PEI)/MWCNT/GC electrode and pristine MWCNT/GC electrode were also prepared. Contrary to conventional GC electrode, all three types of MWCNT modified electrodes (CA/MWCNT/GC, PEI/MWCNT/GC, and pristine MWCNT/GC) can discriminate μM of DA from 1mM AA using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) due to the inherent electrocatalytic effect of MWCNTs. Compared to positively charged PEI/MWCNT/GC and pristine MWCNT/GC electrodes, negatively charged CA/MWCNT/GC electrode remarkably enhanced the electrochemical sensitivity and selectivity of DA, showing the linear relationship between DPV signal and DA concentration in the range of 10-1000nM even in the presence of ~10(5) times concentrated AA, which is attributed to the synergistic effect of the electrostatic interaction between cationic DA molecules and negatively charged MWCNTs and the inherent electrocatalytic property of MWCNT. As a result, the limit of detection (LOD) of DA for CA/MWCNT/GC electrode was 4.2nM, which is 5.2 and 16.5 times better than those for MWCNT/GC electrode and PEI/MWCNT/GC electrode even in the presence of 1mM AA. This LOD value for DA at CA/MWCNT/GC electrode is one of the lowest values compared to the previous reports and is low enough for the early diagnosis of neurological disorder in the presence of physiological AA concentration (0.5mM). In addition, the high selectivity and sensitivity of DA at CA/MWCNT/GC electrode were well kept even in the presence of both 1mM AA and 10μM uric acid (UA) as similar as neurophysiological concentration.
采用简单的超声处理技术,使用无毒的柠檬酸(CA)制备了带负电荷的多壁碳纳米管(MWCNT),用于多巴胺(DA)的电化学检测。通过滴铸法将CA/MWCNT置于玻碳(GC)电极上,然后在高浓度抗坏血酸(AA)存在的情况下进行DA的电化学测定。为了比较电荷对MWCNT表面的影响,还制备了带正电荷的聚乙烯亚胺(PEI)/MWCNT/GC电极和原始MWCNT/GC电极。与传统的GC电极不同,由于MWCNT固有的电催化作用,三种类型的MWCNT修饰电极(CA/MWCNT/GC、PEI/MWCNT/GC和原始MWCNT/GC)均可通过循环伏安法(CV)和差分脉冲伏安法(DPV)将约μM的DA与1 mM的AA区分开来。与带正电荷的PEI/MWCNT/GC电极和原始MWCNT/GC电极相比,带负电荷的CA/MWCNT/GC电极显著提高了DA的电化学灵敏度和选择性,即使在存在约10⁵倍浓度的AA的情况下,DPV信号与DA浓度在10 - 1000 nM范围内仍呈线性关系,这归因于阳离子DA分子与带负电荷的MWCNT之间的静电相互作用以及MWCNT固有的电催化性能的协同效应。结果,CA/MWCNT/GC电极对DA的检测限(LOD)为4.2 nM,即使在存在1 mM AA的情况下,也分别比MWCNT/GC电极和PEI/MWCNT/GC电极的检测限好5.2倍和16.5倍。与先前的报道相比,CA/MWCNT/GC电极对DA的这一LOD值是最低的值之一,并且在生理AA浓度(约0.5 mM)存在的情况下,该值低到足以用于神经疾病的早期诊断。此外,即使在存在1 mM AA和10 μM尿酸(UA)且浓度与神经生理浓度相似的情况下,CA/MWCNT/GC电极对DA的高选择性和灵敏度也能很好地保持。