Signal enhancement on laser desorption/ionization using alkali dihydroxybenzoic acid salts as cationizing agentsMatrix-assisted laser desorption/ionization (MALDI), Biopolymers, synthetic polymers and metal complexes have been successfully analyzed by MALDI-mass spectrometry (MS). [3][4][5][6] For measurement by MALDI-MS, it is necessary that UV-absorbing organic molecules, referred to as the matrix and target analyte, be mixed and deposited on a sample target. This leads to the production of a high intensity of matrix-derived ions and cluster ions in the low-mass region of MALDI spectra and these ions can sometimes interfere with the characterization of low-mass compounds. Various MALDI preparations have been designed to suppress ions from the matrix and enhance analyte ions. [7][8][9][10][11][12][13] At appropriate matrix-to-analyte mixing ratios, the matrix-related ions in MALDI spectra are suppressed.7 Addition of iodine to the matrix reportedly suppresses the signal intensities of the matrix-related ions and increases the analyte ions. 8 Lithium 2,5-dihydroxybenzoate (LiDHB) was shown to be an effective matrix for saturated hydrocarbons and lipids that had previously been difficult to ionize.
9A pre-prepared sample target that was coated with a thin layer of a-cyano-4-hydroxycinnamic acid (CHCA) and nitrocellulose was shown to suppress CHCA signals with no significant loss of analyte sensitivity.
10A sol-gel-derived dihydroxybenzoic acid thin film was reported to facilitate the mass analysis of analytes by laser desorption/ionization with a matrix interference-free background.
11Siuzdak and coworkers developed a matrix-free ionization method and named it laser desorption/ionization on silicon (DIOS We studied the suitability of 2,5-dihydroxybenzoic acid (DHB) salts, NaDHB, LiDHB and NH 4 DHB, as cationizing agents for the analysis of synthetic polymers. We focused on the suppression of matrix-related ions and the enhancement of analyte signals in MALDI and DIOS measurements.Acetonitrile, ethanol, 46% HF, DHB, NaI, LiBr, and CH 3 COONH 4 were purchased from Wako Pure Chemicals (Osaka, Japan). The Na-, Li-and NH 4 -DHB salts were also supplied by Wako Pure Chemicals. Poly-1,4-butyleneglycol adipate acid (BGAA, Mw 1000) was from Sigma-Aldrich (Milwaukee, WI, USA); angiotensin and insulin (human) were from Bachem AG (Bubendorf, Switzerland). Industrial-grade polycaprolactonediol (PCL, Mw 300) and nonylphenolpolyethoxyerate (NP, Mw 2400) were used. Polyethylene glycol (PEG, Mw 1000) was obtained from Wako Pure Chemicals, and polymethylmethacrylate (PMMA, Mw 1400) from Shodex Standard (Shoko, Co., Tokyo, Japan). The structures of the synthetic polymers are shown in Scheme 1. The ntype silicon wafers were obtained from Sumitomo Mitsubishi Silicon Corporation (Tokyo, Japan).DIOS chips were prepared as described previously.8 Briefly, n-type silicon (1 0 0) wafers of resistivity r ¼ 0.008-0.02 Vcm were used. They were anodically etched in a 1:1 (v/v) solution of EtOH/HF (46%) under exposure to white light using a 100 ...