Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry has become an important technique to characterize the chemical structure of industrial polymer materials. MALDI methods have been developed to address a broad variety of different polymer materials containing different chemistries. One of the key aspects of the typical MALDI experiment is the generation of intact ions. The development of Atmospheric Pressure (AP) MALDI quadrupole ion trap (QIT) instruments has opened another channel to obtaining MS/MS experiments for polymer samples. These experiments provide a new method to obtain chemical structure information from MALDI experiments. Collision-Induced Dissociation (CID) provides an improved MALDI MS/MS experiment that can be done on readily available mass spectrometers. AP MALDI QIT techniques have been successfully applied to a variety of synthetic polymers. This work explores the applicability of AP MALDI QIT methods to relatively low molecular weight ethoxylated surfactants. In these experiments we show the CID fragmentation mass spectra on some ethoxylated surfactants, and demonstrate the existence of analyte matrix clusters. [5][6][7]. MALDI can generate important data on the telomer repeat units, end groups, and average molecular weights of these materials. MALDI methods have been developed to address a broad variety of different polymer materials containing different chemistries. One of the key aspects of the typical MALDI experiment is the generation of intact ions. MALDI mass spectra generally show little fragmentation. The production of intact ions is vital for the quantitation of average molecular weights, but limits the amount of chemical structural information that can be obtained from the data.The development of MALDI post-source decay (PSD) techniques has opened a new method to obtain chemical structure information from MALDI experiments [8 -10]. Unfortunately, PSD experiments are relatively crude MS/MS experiments. The range of masses submitted for the fragmentation is broad, the mass resolution and mass accuracy of the fragment spectra is not as good as the MALDI data, and there is very limited control of the energy deposition into the fragmentation process.The development of atmospheric pressure (AP) MALDI instruments has enabled the utilization of different mass analyzers for MALDI [11,12]., One of the key benefits to changing the mass analyzer in a MALDI experiment is to significantly improve the MS/MS capability. A quadrupole ion trap (QIT) mass spectrometer is an excellent choice in this regard. Some early work showed examples of high quality MS/MS experiments on MALDI generated peptides [13][14][15][16]. The ability to analyze synthetic polymers using AP MALDI methods on a QIT have also been demonstrated [17].With a QIT mass spectrometer we can accomplish high quality collision-induced dissociation (CID) MS/ MS. The instrument is capable of selecting an individual ion from the mass spectrum for fragmentation. The fragmentation gas and relative energy can be controlled...