Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, 3-3-35 Yamate-cho, Suita-shi, Osaka, 564-8680 Japan.
Chemistry. 2010 Sep 17;16(35):10832-43. doi: 10.1002/chem.201001038.
We report a new and facile method for synthesizing 3D platinum nanoflowers (Pt Nfs) on a scratched silicon substrate by electroless galvanic displacement and discuss the applications of the Pt Nfs in surface-assisted laser desorption/ionization-mass spectrometry (SALDI-MS). Surface scratching of n-type silicon is essential to induce Pt Nf growth on a silicon substrate (to obtain a Pt Nf silicon hybrid plate) by the galvanic displacement reaction. The Pt Nf silicon hybrid plate showed excellent SALDI activity in terms of the efficient generation of protonated molecular ions in the absence of a citrate buffer. We propose that the acidity of the Si-OH moieties on silicon increases because of the electron-withdrawing nature of the Pt Nfs; hence, proton transfer from the Si-OH groups to the analyte molecules is enhanced, and finally, thermal desorption of the analyte ions from the surface occurs. Signal enhancement was observed for protonated molecular ions produced from a titania nanotube array (TNA) substrate on which Pt nanoparticles had been photochemically deposited. Moreover, surface modification of the Pt Nf silicon hybrid plate by perfluorodecyltrichlorosilane (FDTS) (to obtain an FDTS-Pt Nf silicon hybrid plate) was found to facilitate soft SALDI of labile compounds. More interestingly, the FDTS-Pt Nf silicon hybrid plate acts 1) as a high-affinity substrate for phosphopeptides and 2) as a SALDI substrate. The feasibility of using the FDTS-Pt Nf silicon hybrid plate for SALDI-MS has been demonstrated by using a β-casein digest and various analytes, including small molecules, peptides, phosphopeptides, phospholipids, carbohydrates, and synthetic polymers. The hybridization of Pt Nfs with a scratched silicon substrate has been found to be important for achieving excellent SALDI activity.
我们报告了一种新的简便方法，通过无电置换反应在划痕硅衬底上合成 3D 铂纳米花（Pt Nfs），并讨论了 Pt Nfs 在表面辅助激光解吸/电离-质谱（SALDI-MS）中的应用。n 型硅的表面划痕对于通过置换反应在硅衬底上诱导 Pt Nf 生长（获得 Pt Nf 硅杂化板）是必不可少的。Pt Nf 硅杂化板在没有柠檬酸盐缓冲液的情况下，表现出优异的 SALDI 活性，能够有效地生成质子化分子离子。我们提出，由于 Pt Nfs 的吸电子性质，硅上的 Si-OH 基团的酸性增加；因此，质子从 Si-OH 基团转移到分析物分子增强，最终，分析物离子从表面发生热解吸。从经光化学沉积 Pt 纳米粒子的 TiO2 纳米管阵列（TNA）衬底上产生的质子化分子离子的信号增强得到了观察。此外，发现通过全氟癸基三氯硅烷（FDTS）对 Pt Nf 硅杂化板进行表面修饰（以获得 FDTS-Pt Nf 硅杂化板）有助于不稳定化合物的软 SALDI。更有趣的是，FDTS-Pt Nf 硅杂化板 1）作为磷肽的高亲和力衬底，2）作为 SALDI 衬底。通过使用β-酪蛋白消化物和各种分析物，包括小分子、肽、磷肽、磷脂、碳水化合物和合成聚合物，已经证明了 FDTS-Pt Nf 硅杂化板用于 SALDI-MS 的可行性。Pt Nfs 与划痕硅衬底的杂交对于实现优异的 SALDI 活性非常重要。
