Characterization of an insoluble poly(9,9-diphenyl-2,7-fluorene) by solvent-free sample preparation for MALDI-TOF mass spectrometry.
Characterization of an insoluble poly(9,9-diphenyl-2,7-fluorene) by solvent-free sample preparation for MALDI-TOF mass spectrometry.
复制标题
通过 MALDI-TOF 质谱法的无溶剂样品制备表征不溶性聚（9,9-二苯基-2,7-芴）。
作者：
S. Trimpin;A. Grimsdale;H. Räder;K. Müllen
基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF MS）的无溶剂样品制备的应用程序允许的聚（9，9-二苯基芴），以前阻碍了缺乏合适的表征方法的不溶性馏分的表征。MALDI质谱分析给出了有价值的非均相聚合过程的聚合物的不溶性高分子量馏分的机械信息。即使在这种刚性骨架分析物的温和解吸和电离条件下出现的碎片也被鉴定为大体积苯基侧基的多重损失，并且可以通过应用新的MALDI基质7，7，8，8-四氰基醌二甲烷来避免。一个专门的碎片研究postsource衰变MALDI-TOF MS揭示了分子量依赖性的变化，从一个排他性的分裂侧基从长的聚合物链的聚合物主链的短聚合物链的额外分裂的碎片机制。
The application of solvent-free sample preparation for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) allowed the characterization of an insoluble fraction of poly(9,9-diphenylfluorene) that was previously hindered by the lack of suitable characterization methods. The MALDI mass spectrometric analysis gives valuable mechanistic information about the heterogeneous polymerization process of the insoluble high molecular weight fraction of the polymer. The fragmentation appearing even under moderate desorption and ionization conditions of this rigid backbone analyte is identified as a multiple loss of the bulky phenyl side groups and can be avoided by applying the new MALDI matrix 7,7,8,8-tetracyanoquinodimethane. A specialized fragmentation study by postsource decay MALDI-TOF MS reveals a molecular weight dependent change in fragmentation mechanism from an exclusive cleavage of side groups from long polymer chains to an additional cleavage of the polymer backbone of short polymer chains.