Department of Analytical Chemistry, K.N. Toosi University of Technology, Tehran, Iran.
Department of Analytical Chemistry, K.N. Toosi University of Technology, Tehran, Iran.
Anal Chim Acta. 2020 Sep 22;1131:90-101. doi: 10.1016/j.aca.2020.07.053. Epub 2020 Jul 30.
Herein, we applied a simple electrosynthesis process to deposit nickel-iron layered double hydroxides (NiFe LDH) on the surface of copper hydroxide (Cu(OH)) needle-shaped nanoarrays and introduce a new sorbent for thin-film solid phase microextraction (TF-SPME). For this purpose, the nanoarrays were grown via electrochemical anodization on a copper foil's surface and then modified with NiFe LDH. The synthesized sorbent was characterized by field emission-scanning electron microscopy, Brunauer-Emmett-Teller (BET), and Barrett-Joiner-Halenda (BJH) analysis, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The Cu(OH)-NiFe LDH based TF-SPME method was used to measure antifungal drugs in veterinary plasma samples followed by HPLC-UV analysis. The effects of various parameters in the extraction efficiency, including pH (5.0), extraction time (20 min), stirring rate (500 rpm), and salt effect (5.0%), type of eluent (acetonitrile), eluent volume (100 μL) and desorption time (5 min) were thoroughly optimized. Under the optimum conditions, limits of detection for ketoconazole, clotrimazole, and miconazole were obtained below 10 ng mL. Intra-day, inter-day and film-to-film RSDs% were obtained less than 6.2%, 7.3% and 7.0%, respectively. Moreover, calibration plots were linear from 30 to 5000 ng mL for ketoconazole, 8.0-1000 ng mL for clotrimazole, and 15-1000 ng mL for miconazole, with determination coefficients between 0.9937 and 0.9971. Finally, good relative recoveries (%) in the range of 85-97% were obtained for measuring trace amounts of antifungal drugs in dogs' plasma samples. As a result, the method can be considered as an appropriate alternative to the conventional sample preparation methods for measuring trace amounts of antifungal drugs in biological samples.
在此，我们应用一种简单的电合成工艺在铜氢氧化物（Cu(OH)）针状纳米阵列的表面沉积镍铁层状双氢氧化物（NiFe LDH），并引入一种新的用于薄膜固相微萃取（TF-SPME）的吸附剂。为此，通过电化学阳极氧化在铜箔表面生长纳米阵列，然后用 NiFe LDH 进行修饰。通过场发射扫描电子显微镜、Brunauer-Emmett-Teller（BET）和 Barrett-Joiner-Halenda（BJH）分析、能量色散 X 射线光谱和 X 射线衍射对合成的吸附剂进行了表征。采用基于 Cu(OH)-NiFe LDH 的 TF-SPME 方法测定兽医血浆样品中的抗真菌药物，然后进行 HPLC-UV 分析。优化了萃取效率的各种参数，包括 pH（5.0）、萃取时间（20 分钟）、搅拌速度（500 rpm）和盐效应（5.0%）、洗脱剂类型（乙腈）、洗脱剂体积（100 μL）和洗脱时间（5 分钟）。在最佳条件下，酮康唑、克霉唑和咪康唑的检测限均低于 10 ng mL。日内、日间和膜间 RSD%分别小于 6.2%、7.3%和 7.0%。此外，酮康唑的校准曲线在 30-5000 ng mL 范围内线性良好，克霉唑的校准曲线在 8.0-1000 ng mL 范围内线性良好，咪康唑的校准曲线在 15-1000 ng mL 范围内线性良好，相关系数在 0.9937 到 0.9971 之间。最后，在犬血浆样品中测定痕量抗真菌药物时，获得了 85-97%的良好相对回收率（%）。结果表明，该方法可作为测定生物样品中痕量抗真菌药物的常规样品制备方法的一种合适替代方法。
