RESUMO
Resonance enhanced multiphoton ionization spectroscopy (REMPI) generates simultaneous vibronic spectroscopy and fragment free mass spectrometry to identify molecules within a complex matrix. We combined laser desorption with REMPI spectroscopy to study organic residues within pottery sherds from Maya vessels (600-900 CE) and Mississippian vessels (1100-1200 CE), successfully detecting three molecular markers, caffeine, theobromine, and theophylline, associated with the use of cacao. This analytical approach provides a high molecular specificity, based on both wavelength and mass identification. At the same time, the high detection limit allows for direct laser desorption from sherd scrapings, avoiding the need for extracting organic constituents from the sherd matrix.
RESUMO
The mechanism of inhibition of insulin-based amyloid gel formation by metal derivatives of tetrakis(4-sulfonatophenyl)porphyrin has been investigated. Time-course UV/vis measurements in conjunction with atomic force microscopy (AFM) were used to study the correlation between observed kinetics and amyloid structure for various concentration ranges of added metalloporphyrins. Observed structures include fibrils as well as circular, ring-like structures formed as a result of the interaction of insulin with porphyrin. In addition, binding studies demonstrate that the effectiveness of inhibition of the various metalloporphyrins is directly related to the strength of binding to insulin. It is suggested that both the electron distribution in the porphyrin core and the tendency to form porphyrin dimers affect both the structure of amyloid formed and the kinetic profile of the reaction.
