Department of Analytical Chemistry, Faculty of Pharmacy, Karadeniz Technical University, Trabzon, Turkey.
Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Karadeniz Technical University, Trabzon, Turkey.
J Chromatogr A. 2021 Apr 12;1642:462007. doi: 10.1016/j.chroma.2021.462007. Epub 2021 Feb 18.
In this study, a simple, green, and reliable method combining vortex-assisted liquid-liquid microextraction based on in situ formation of a novel hydrophobic natural deep eutectic solvent (NADES-VA-LLME) and high-performance liquid chromatography (HPLC) was developed for the determination of metoprolol and propranolol in water samples. The novel NADES was synthesized in situ within only 20 s by subjecting the water sample containing azelaic acid and thymol to microwave irradiation at 50 ˚C. Initial studies indicated that a 17:1 ratio of thymol to azelaic acid yielded the highest response for analytes. The influence of 7 parameters, including NADES volume, salt amount, sample pH, vortex time, centrifugation time, microwave time, and temperature, were screened using a 2 fractional factorial design. The obtained significant parameters were optimized by response surface methodology employing a Box-Behnken design. The method displayed satisfactory linearity (r=0.9996) for metoprolol and propranolol with limits of detection of 0.2 and 0.1 µg/L, respectively. The relative standard deviation at 2.5, 40, and 80 µg/L levels was lower than 6%, with accuracy in the range of 90.8-100.2%. Enrichment factors were 147.0 and 144.4 for metoprolol and propranolol, respectively. This study demonstrates that the developed in situ NADES-VA-LLME-HPLC technique can be considered as a fast and environmentally friendly alternative for isolation/preconcentration of β-blockers from water samples.
在这项研究中，开发了一种简单、绿色、可靠的方法，结合了基于新型疏水天然深共晶溶剂（NADES）就地形成的涡旋辅助液 - 液微萃取（VA-LLME）和高效液相色谱（HPLC），用于测定水样中的美托洛尔和普萘洛尔。新型 NADES 是通过在 50°C 下用微波辐射仅 20 秒，将含有壬二酸和百里香酚的水样进行处理，就地合成的。初步研究表明，百里香酚与壬二酸的比例为 17:1 时，对分析物的响应最高。使用 2 分数阶因子设计筛选了 7 个参数的影响，包括 NADES 体积、盐量、样品 pH 值、涡旋时间、离心时间、微波时间和温度。使用 Box-Behnken 设计的响应面法优化了获得的显著参数。该方法对美托洛尔和普萘洛尔表现出令人满意的线性（r=0.9996），检测限分别为 0.2 和 0.1 µg/L。在 2.5、40 和 80 µg/L 水平下的相对标准偏差低于 6%，准确度在 90.8-100.2%范围内。美托洛尔和普萘洛尔的富集因子分别为 147.0 和 144.4。本研究表明，开发的原位 NADES-VA-LLME-HPLC 技术可以被认为是一种从水样中分离/预浓缩β受体阻滞剂的快速且环保的替代方法。
