Department of Chemistry, University of Virginia, Charlottesville, 22904, USA.
Anal Chem. 2012 Sep 18;84(18):7816-22. doi: 10.1021/ac301445w. Epub 2012 Aug 24.
Carbon nanotube (CNT) modification of microelectrodes can result in increased sensitivity without compromising time response. However, dip coating CNTs is not very reproducible and the CNTs tend to lay flat on the electrode surface which limits access to the electroactive sites on the ends. In this study, aligned CNT forests were formed using a chemical self-assembly method, which resulted in more exposed CNT ends to the analyte. Shortened, carboxylic acid functionalized single-walled CNTs were assembled from a dimethylformamide (DMF) suspension onto a carbon-fiber disk microelectrode modified with a thin iron hydroxide-decorated Nafion film. The modified electrodes were highly sensitive, with 36-fold higher oxidation currents for dopamine using fast-scan cyclic voltammetry than bare electrodes and 34-fold more current than electrodes dipped in CNTs. The limit of detection (LOD) for dopamine was 17 ± 3 nM at a 10 Hz repetition rate and 65 ± 7 nM at 90 Hz. The LOD at 90 Hz was the same as a bare electrode at 10 Hz, allowing a 9-fold increase in temporal resolution without a decrease in sensitivity. Similar increases were observed for other cationic catecholamine neurotransmitters, and the increases in current were greater than for anionic interferents such as ascorbic acid and 3,4-dihydroxyphenylacetic acid (DOPAC). The CNT forest electrodes had high sensitivity at 90 Hz repetition rate when stimulated dopamine release was measured in Drosophila . The sensitivity, temporal resolution, and spatial resolution of these CNT forest modified disk electrodes facilitate enhanced electrochemical measurements of neurotransmitter release in vivo.
碳纳米管(CNT)修饰微电极可以在不影响时间响应的情况下提高灵敏度。然而,浸涂 CNT 不太可重复,并且 CNT 往往平铺在电极表面上,这限制了对末端电活性位点的访问。在这项研究中,使用化学自组装方法形成了取向的 CNT 森林,这导致更多的 CNT 末端暴露于分析物。从二甲基甲酰胺(DMF)悬浮液中组装了短的、羧酸官能化的单壁 CNT,组装到经过薄的氧化铁修饰的 Nafion 膜修饰的碳纤维盘微电极上。修饰后的电极具有很高的灵敏度,使用快速扫描循环伏安法检测多巴胺时,氧化电流比裸电极高 36 倍,比浸涂 CNT 的电极高 34 倍。多巴胺的检测限(LOD)在 10 Hz 重复率下为 17 ± 3 nM,在 90 Hz 下为 65 ± 7 nM。90 Hz 下的 LOD 与 10 Hz 下的裸电极相同,在不降低灵敏度的情况下将时间分辨率提高了 9 倍。其他阳离子儿茶酚胺神经递质也观察到类似的电流增加,并且与抗坏血酸和 3,4-二羟基苯乙酸(DOPAC)等阴离子干扰物相比,电流增加更大。当在果蝇中测量多巴胺释放时,这些 CNT 森林修饰的盘电极在 90 Hz 重复率下具有高灵敏度。这些 CNT 森林修饰的盘电极的灵敏度、时间分辨率和空间分辨率有助于增强体内神经递质释放的电化学测量。