Nagy Tibor, Kuki Ákos, Nagy Lajos, Zsuga Miklós, Kéki Sándor
Department of Applied Chemistry, University of Debrecen, Egyetem tér 1, Debrecen, H-4032, Hungary.
J Mass Spectrom. 2018 Mar;53(3):240-246. doi: 10.1002/jms.4061.
Direct analysis in real-time mass spectrometry (DART-MS) with in situ silylation was used for the rapid analysis of the flavonoids silybin ((2R,3R)-3,5,7-trihydroxy-2-[3-(4-hydroxy-3-methoxyphenyl)-2-hydroxymethyl-2,3-dihydrobenzo[1,4]dioxin-6-yl]chroman-4-one) and rutin (quercetin-3-O-rutinoside). Three different derivatization reagents, hexamethyldisilazane/trimethylchlorosilane/pyridine (HMDS/TMCS/pyridine), N,O-bis(trimethylsilyl)acetamide/trimethylchlorosilane/N-trimethylsilyimidazole (BSA/TMCS/TMSI), and N,O-bis(trimethylsilyl)trifluoroacetamide/trimethylchlorosilane (BSTFA/TMCS), were applied. Silybin and rutin were detected with various degrees of silylation, and the formation of dimers with pyridine and imidazole was also observed. HMDS/TMCS/pyridine was the best choice for the DART-MS analysis of silybin, and BSA/TMCS/TMSI was the most effective for the detection of rutin. The effects of the DART source temperature on desorption, ionization, in-source fragmentation, dimer formation, and hydrolysis of the trimethylsilyl groups were also studied. In addition, the collision-induced dissociation properties of the derivatized silybin and rutin were explored. With our in situ silylation method, the derivatized bioactive compounds in intact medical pills could also be detected by DART-MS.
采用原位硅烷化实时直接分析质谱法（DART-MS）对黄酮类化合物水飞蓟宾（(2R,3R)-3,5,7-三羟基-2-[3-(4-羟基-3-甲氧基苯基)-2-羟甲基-2,3-二氢苯并[1,4]二恶英-6-基]色满-4-酮）和芦丁（槲皮素-3-O-芸香糖苷）进行快速分析。应用了三种不同的衍生化试剂，即六甲基二硅氮烷/三甲基氯硅烷/吡啶（HMDS/TMCS/吡啶）、N,O-双(三甲基硅基)乙酰胺/三甲基氯硅烷/N-三甲基硅基咪唑（BSA/TMCS/TMSI）和N,O-双(三甲基硅基)三氟乙酰胺/三甲基氯硅烷（BSTFA/TMCS）。检测到水飞蓟宾和芦丁具有不同程度的硅烷化，还观察到与吡啶和咪唑形成二聚体的情况。HMDS/TMCS/吡啶是水飞蓟宾DART-MS分析的最佳选择，而BSA/TMCS/TMSI对芦丁的检测最为有效。还研究了DART源温度对解吸、电离、源内裂解、二聚体形成以及三甲基硅基水解的影响。此外，还探索了衍生化水飞蓟宾和芦丁的碰撞诱导解离特性。采用我们的原位硅烷化方法，完整药丸中的衍生化生物活性化合物也可通过DART-MS进行检测。
