Fallahpour Nastaran, Charabeh Atefeh, Ebrahimi Bahram
Department of Chemistry, Sa. C., Islamic Azad University, Sanandaj, Iran.
Department of Chemistry, Sa. C., Islamic Azad University, Sanandaj, Iran.
Anal Chim Acta. 2025 Oct 15;1371:344430. doi: 10.1016/j.aca.2025.344430. Epub 2025 Jul 14.
In recent decades, introducing new fibers has improved the SPME method. Commercial fibers are expensive, have low stability and selectivity, and usually sorption occurs by non-selective mechanisms. Various techniques have been presented for the production of homemade fibers. Most of these methods require several steps to prepare the supports to be coated. The preparation of supports for coating is time-consuming, requires numerous reagents, and does not allow the mass production of fibers. Therefore, the search is ongoing to produce new SPME fibers with selective extraction behavior, easy preparation, low cost, and less use of chemical reagents.
We present a straightforward, low-cost, green, and fast method to produce new SPME fibers based on microwave modification and polymerization of pencil lead support. The pencil lead structure was modified using microwave irradiation and then coated with a ketoprofen-molecularly imprinted polymer. After locating the 30 numbers of pencil lead support on the glassy holder, modification and polymerization of the supports were implemented overall at 5 min. The fibers were characterized using FT-IR, SEM, TGA, and BET analysis, showing the successful coating of the supports. The produced fibers presented selective extraction behavior for ketoprofen in the presence of similar NSAIDs with good repeatability. The detection limits for ketoprofen in plasma and urine samples were 8.25 and 16.34 ng mL, respectively. A pharmacokinetic study showed the fibers' clinical applicability, revealing a maximum plasma concentration of 15.69 μg/mL, a time to reach this concentration of 2 h, and a half-life of 2.66 h.
This study represents a fast, precise, and simple method for mass-producing new SPME fibers (MIP coating) using microwave irradiation. Except for on-fiber derivatization, the introduced method doesn't need chemical reagents or extra steps. The fibers' capability was proved in urine and plasma samples for selective ketoprofen bioanalysis and pharmacokinetic study.
近几十年来，新型纤维的引入改进了固相微萃取（SPME）方法。商业纤维价格昂贵，稳定性和选择性低，且通常通过非选择性机制进行吸附。已提出了多种制备自制纤维的技术。这些方法大多需要几个步骤来制备待涂层的载体。涂层载体的制备耗时，需要大量试剂，且不允许大规模生产纤维。因此，人们一直在寻找具有选择性萃取行为、制备简便、成本低且化学试剂用量少的新型SPME纤维。
我们提出了一种基于铅笔芯载体的微波改性和聚合来生产新型SPME纤维的直接、低成本、绿色且快速的方法。使用微波辐射对铅笔芯结构进行改性，然后用酮洛芬分子印迹聚合物进行涂层。在将30根铅笔芯载体放置在玻璃支架上后，载体的改性和聚合在5分钟内全部完成。使用傅里叶变换红外光谱（FT-IR）、扫描电子显微镜（SEM）、热重分析（TGA）和比表面积分析（BET）对纤维进行表征，结果表明载体涂层成功。所制备的纤维在存在类似非甾体抗炎药（NSAIDs）的情况下对酮洛芬具有选择性萃取行为，且重复性良好。血浆和尿液样品中酮洛芬的检测限分别为8.25和16.34 ng/mL。一项药代动力学研究表明了这些纤维的临床适用性，显示最大血浆浓度为15.69 μg/mL，达到该浓度的时间为2小时，半衰期为2.66小时。
本研究代表了一种使用微波辐射大规模生产新型SPME纤维（分子印迹聚合物涂层）的快速、精确且简单的方法。除了纤维上衍生化外，所介绍的方法不需要化学试剂或额外步骤。这些纤维在尿液和血浆样品中的选择性酮洛芬生物分析和药代动力学研究中的能力得到了证明。
