MALDI机理介绍.pdfVIP

MALDI and Related Methods: A Solved Problem or Still a Mystery? Richard Knochenmuss Tofwerk AG Thun, Switzerland rknochenmuss@gmx.net Abstract MALDI ionization mechanisms remain a topic of controversy. Some of the major modern models are compared, with emphasis on the those of the author. Primary formation, secondary reaction and loss mechanisms are considered. Keywords MALDI, primary and secondary ionization, recombination, ablation Introduction A variety of processes have been suggested to contribute to ion formation in MALDI.[1] While many are no longer under active consideration, consensus has also not been reached. Because MALDI is a multifaceted process, it is easy to loose sight of one aspect while investigating another, but all aspects need to be taken into account, to develop models that are consistent with the available data. This paper presents an overview of key aspects of MALDI with ultraviolet laser excitation, and compares some models, with emphasis on those of the author. Computational Methods The rate equation model has been described in detail in refs. [2-4]. Briefy, it is a system of coupled differential equations for the evolution of neutrals, positive and negative ions, of both matrix and up to two analytes. Ionization can be either via pooling of matrix excitons, thermal, or preformed. Nonionic excited states of the matrix are treated, but the analytes are 1 assumed not to absorb the laser light. Forward and backward ion-molecule and ion-ion reactions are treated with an Arrhenius approach, using nonlinear free energy relationships to estimate activation energies. All reactions are modulated by the temperature and pressure evolution of the plu