Ion pairing of nucleotides with surfactants for enhanced sensitivity in liquid matrix assisted secondary ion mass spectrometry Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/4m90dz782

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  • In particle induced desorption-ionization mass spectrometry the strength of an analyte's signal under a given set of bombardment conditions is usually considered to be representative of the analytes relative surface activity. This rationale is generally used to explain differences in the technique's sensitivity between and within various classes of compound. In liquid matrix assisted secondary ion mass spectrometry (SIMS) sensitivity enhancement of ionic analytes by pairing with surface active counterions has been demonstrated by several groups. This technique has been utilized in this work to achieve a 10,000 fold enhancement in the signal for ATP on a double focusing magnetic sector instrument and to detect femtomole quantities of nucleoside monophosphates on a time-of-flight instrument. The analyte's signal, however, is dependent on both the analyte bulk concentration and that of the surfactant. Additionally, the surfactant concentration that produces the maximum analyte signal changes with the analyte concentration. In this study, this phenomenon has been modeled in terms of conventional solution equilibria and surface chemical principles. It is assumed that the initial surface composition and the bulk concentration are the boundary conditions of a steady state established by the competing processes of surface sputtering and surface replenishment from the bulk during analysis. Calculated surface excesses correlate well with observed relative ion intensities, suggesting that equilibrium conditions are approached in the sample matrices despite the outwardly dynamic nature of the sputtering processes.
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  • description.provenance : Approved for entry into archive by Patricia Black(patricia.black@oregonstate.edu) on 2012-12-21T20:37:27Z (GMT) No. of bitstreams: 1 PavlovichJamesGilbert1994.pdf: 3579557 bytes, checksum: ae84b932af6a897a93388da9d1ac99da (MD5)
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