文献类型：期刊文献

英文题名：Exploring the Potential of Chemically Matched Fragments as Internal Standards for Quantitative SERS with Panobinostat

作者：Huang, Yiming[1];Xu, Yikai[2,3];Li, Chunchun[4];Bell, Steven E. J.[1]

机构：[1]Queens Univ, Sch Chem & Chem Engn, Belfast BT9 5AG, North Ireland;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China

年份：2025

卷号：97

期号：34

起止页码：18490

外文期刊名：ANALYTICAL CHEMISTRY

收录：;EI(收录号：20253619110659);WOS:【SCI-EXPANDED(收录号:WOS:001554784500001)】；

基金：Y.X. acknowledges the National Natural Science Foundation of China (22125803, 22020102006). C.L. acknowledges the Shanghai Pujiang Program (23PJ1409000).

语种：英文

外文关键词：Calibration - Colloids - Patient monitoring - Raman spectroscopy

摘要：Surface-enhanced Raman spectroscopy (SERS) has great potential for therapeutic drug monitoring (TDM) due to its high sensitivity; however, achieving accurate and robust quantitative data remains challenging. The most effective approach for quantitative SERS is to use internal standards (IS). Isotopologues are particularly effective; however, these or closely related analogues of the target compound are often unavailable. We have addressed this problem by using fragments of the target compound as the IS. Here, 2-methylindole (2-MI) was identified as the most suitable fragment for Panobinostat (Pano). Tests with an enhancing colloid that degraded significantly over a 4-week period showed that the 2-MI IS allowed changes in the absolute intensity of the Pano signal over time to be corrected and that the standard error achieved with the degrading enhancing medium matched that of results obtained with the fresh colloid. The calibration range could be extended by using either low (4 x 10-7 M) or high (10-5 M) concentrations of 2-MI, both of which gave linear log/log Pano calibration curves (R 2 = 0.993 and 0.998, respectively) although these curves had different slopes. In contrast, thiophenol (TP), a nonchemically matched IS, gave reasonable results at a low (10-6 M) concentration (R 2 = 0.942) but completely failed at a high (10-5 M) concentration due to surface saturation. These findings can be rationalized using a model where, at submonolayer concentrations, both the target and IS adsorb to the nanoparticle surface in proportion to their concentrations; however, at higher concentrations, competition for active sites on surface alters the relative intensities observed. This fragment-based approach significantly increases the availability of chemically matched IS for large target molecules and therefore significantly broadens the range of compounds where robust quantitative SERS analysis is possible.