RESUMEN
We present a cryogenic mass spectrometry protocol with the capability to detect peptides in the attomole dilution range from ice films. Our approach employs femtosecond laser pulses and implements neither substrate modification nor proton donor agents in the aqueous solution, known to facilitate analyte detection in mass spectrometry. In a systematic study, we investigated the impact of temperature, substrate composition, and irradiation wavelength (513 and 1026 nm) on the bradykinin signal onset. Our findings show that substrate choice and irradiation wavelength have a minor impact on signal intensity once the preparation protocol is optimized. However, if the temperature is increased from -140 to 0 °C, which is accompanied by ice film thinning, a somehow complex picture of analyte desorption and ionization is recognizable, which has not been described in the literature yet. Under cryogenic conditions (-140 °C), obtaining a signal is only possible from isolated sweet spots across the film. If the thin ice film is between -100 and -70 °C of temperature, these sweet spots appear more frequently. Ice sublimation triggered by temperatures above -70 °C leads to an intense and robust signal onset that could be maintained for several hours. In addition to the above findings, we notice that a vibrant fragmentation pattern produced is strikingly similar with both wavelengths. Our findings suggest that while following an optimized protocol, femtosecond mass spectrometry has excellent potential to analyze small organic molecules and peptides with a mass range of up to 2.5 kDa in aqueous solution without any matrix, as employed in matrix-assisted laser desorption/ionization (MALDI) or any substrate surface modification, found in surface-assisted laser desorption/ionization (SALDI).
Asunto(s)
Bradiquinina , Protones , Rayos Láser , Péptidos/química , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodosRESUMEN
Spatially resolved measurements of the magnetization dynamics on a thin CoFeB film induced by an intense laser pump-pulse reveal that the frequencies of resulting spin-wave modes depend strongly on the distance to the pump center. This can be attributed to a laser generated temperature profile. We determine a shift of 0.5 GHz in the spin-wave frequency due to the spatial thermal profile induced by the femtosecond pump pulse that persists for up to one nanosecond. Similar experiments are presented for a magnonic crystal composed of a CoFeB-film based antidot lattice with a Damon Eshbach mode at the Brillouin zone boundary and its consequences are discussed.