Wu Hsin-Pin, Yu Cheng-Ju, Lin Chin-Yu, Lin Yen-Hsiu, Tseng Wei-Lung
Department of Chemistry, National Sun Yat-sen University, Taiwan.
J Am Soc Mass Spectrom. 2009 May;20(5):875-82. doi: 10.1016/j.jasms.2009.01.002. Epub 2009 Jan 9.
Citrate-capped gold nanoparticles (AuNPs) serve as matrices for the determination of biomolecules in a high-salt solution through matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the case of using 2,5-dihydroxybenzoic acid (2,5-DHB) as a matrix, the signal intensities of neutral steroids were severely suppressed in a high-salt solution. A high concentration of NaCl caused the formation of the sodium adduct ions during the desorption/ionization process, resulting in a decrease of the signal intensities of the protonated ions. In comparison, by applying AuNP-assisted LDI-TOF-MS, the signal intensities of neutral steroids remained almost constant when the concentration of NaCl was increased to 500 mM. Because the use of citrate-capped AuNPs as matrices primarily offers alkali metal ion adducts, AuNP matrices have a higher tolerance to high NaCl concentrations relative to that of 2,5-DHB matrices. The relevant phenomena are also discovered in the case of analysis of neutral carbohydrate, monosialoganglioside, indolamine, and angiotensin I. The quantification of small molecules in a high-salt solution has been accomplished by AuNP-assisted LDI-TOF-MS coupled to a unique sample preparation, in which samples are deposited onto the sample plate before AuNPs. The present method has been further applied to the determination of urea, creatinine, uric acid, and glucose in a urine sample.
柠檬酸盐包覆的金纳米颗粒(AuNPs)作为基质,通过基质辅助激光解吸/电离飞行时间质谱(MALDI-TOF-MS)用于在高盐溶液中测定生物分子。在使用2,5-二羟基苯甲酸(2,5-DHB)作为基质的情况下,中性类固醇的信号强度在高盐溶液中受到严重抑制。高浓度的氯化钠在解吸/电离过程中导致钠加合物离子的形成,从而导致质子化离子的信号强度降低。相比之下,通过应用AuNP辅助的激光解吸电离飞行时间质谱(LDI-TOF-MS),当氯化钠浓度增加到500 mM时,中性类固醇的信号强度几乎保持不变。由于使用柠檬酸盐包覆的AuNPs作为基质主要提供碱金属离子加合物,相对于2,5-DHB基质,AuNP基质对高氯化钠浓度具有更高的耐受性。在分析中性碳水化合物、单唾液酸神经节苷脂、吲哚胺和血管紧张素I的情况下也发现了相关现象。通过AuNP辅助的LDI-TOF-MS结合独特的样品制备方法实现了高盐溶液中小分子的定量,其中样品在AuNPs之前沉积在样品板上。本方法已进一步应用于尿液样品中尿素、肌酐、尿酸和葡萄糖的测定。