ABSTRACT
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 ß-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.
ABSTRACT
The pyrolytic highly oriented graphite polymer film (PGS) was first employed to analyze low-mass analytes in environmental analysis by surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). PGS is a synthetic uniform and highly oriented graphite polymer film with high thermal anisotropic conductivity. We have found that negative ion mode SALDI-MS using oxidized PGS (PGS-SALDI-MS) can be used to detect [M-H]- ions from perfluorooctanoic acid (PFOA) and other perfluoroalkylcarboxylic acids when the PGS surface is modified with the cationic polymer polyethyleneimine (PEI). The signal intensity of PFOA when employing the PEI modification showed a ten-fold increase over that obtained from desorption/ionization on porous silicon (DIOS). PFOA was quantified using PGS-SALDI-MS and the calibration curve showed a wide linear dynamic range of response (20-1000 ppb). The combination of atmospheric pressure ionization and PGS (AP-PGS-SALDI) showed greater signal intensity than vacuum PGS-SALDI for deprotonated PFOA. Several other environmentally important chemicals, including perfluoroalkylsulfonic acid, pentachlorophenol, bisphenol A, 4-hydroxy-2-chlorobiphenyl, and benzo[a]pyrene, were also successfully used to evaluate PGS-SALDI-MS. In addition, we found that nonafluoro-1-butanesulfonic acid was able to produce protonated peptides in positive ion PGS-SALDI-MS, but that perfluoropentanoic acid and trifluoroacetic acid were not. It is suggested that perfluoroalkylsulfonic acids are better protonating agents than perfluoroalkylcarboxylic acids in SALDI-MS.
