Hybrid Surface Design of Organosilica Films for Laser Desorption/Ionization Mass Spectrometry: Low Free Energy Surface with Interactive Sites.

Laser desorption/ionization mass spectrometry (LDI-MS) assisted by solid substrates is useful for the facile and rapid analysis of low-molecular-weight compounds. The LDI performance of solid substrates depends on not only a surface morphology but also the surface functionalities dominating the surface-analyte interactions. In this study, we propose a hybrid surface design for LDI substrates, realizing both weak surface-analyte interaction and homogeneous distribution of analytes. The hybrid surface consisted of a mixture of fluoroalkylsilane (FAS), SiO2, and TiO2 and was formed on organosilica substrates containing UV-laser-absorbing naphthalimide moieties. To investigate the surface interactions, the hybrid surface as well as conventional hydrophobic surfaces treated with FAS only were prepared on flat organosilica films. Contact angle measurements and surface free energy analysis showed that the hybrid surface exhibited the highest hydrophobicity, while the contribution of the polar and hydrogen bonding terms in the surface free energy was clearly observed. The organosilica film with the hybrid surface demonstrated significant LDI performance for the detection of biorelated compounds (e.g., peptides, phospholipids, and medicines), and a high detection ability was particularly observed for peptides. The substrate surface promoted the desorption/ionization of analytes through a low surface free energy and uniform distribution of the analytes due to the interactive sites. The hybrid surface design was then applied to a nanostructured organosilica substrate consisting of a base film and a nanoparticle layer. The signal intensity of a peptide was further improved approximately 3-fold owing to the increased surface area of the nanostructured substrate, and the limit of detection reached the subfemtomole order. Our hybrid surface design is expected to improve the LDI performance of various nanostructured solid substrates.