| This dissertation describes the physical organic study of reactions on self-assembled monolayers of alkanethiolate on gold using SAMDI mass spectrometry (self-assembled monolayers for matrix assisted laser esorption / ionization time-of-flight mass spectrometry) as the major analysis tool to characterize surface reactions. The rapid detection of reaction products and semi-quantitative measurement of reaction yields enable the study of surface kinetics demonstrated with two examples. One is the nucleophilic substitution of halide and the other is an enzymatic reaction catalyzed by Abl kinase and a phosphatase. In both reactions, the kinetics departed substantially from their better understood solution phase analogues. In addition, combing the miniaturized scale of monolayer reactions and label-free detection of SAMDI, a high-throughput screening for an organic reaction optimization was developed, which allowed for the examination of 1800 reaction conditions within hours, demonstrating the potential of the application of SAMDI MS in high-throughput development of organic reaction parameters. |
