Enhanced and Selective MALDI-MS Detection of Peptides via the Nanomaterial-Dependent Coffee Ring Effect

Nanomaterials have been explored as alternative matrices in MALDI-MS to overcome some of the limitations of conventional matrices. Recently, we demonstrated a new means by which nanomaterials can improve peptide ionization and detection in MALDI-MS analyses by exploiting the tendency of nanomaterials to form "coffee rings" upon drying from liquids. In the current work, we investigate how nanomaterial size and composition affect the signal enhancement of peptides through the coffee-ring effect. From studies of eight different types of nanomaterials ranging in size and composition, we find that most nanomaterials can provide signal enhancement ranging from 2- to 10-fold for individual peptides, as long as a coffee ring is formed. However, when a mixture of peptides is present in a sample, the signal enhancement is the greatest for peptides whose net charge is complementary to the nanomaterial's surface charge. These results suggest that careful design of NM surface properties could allow for selective, enhanced MALDI-MS detection of specific peptides in complex mixtures.