Pulse laser-induced fragmentation of carbon quantum dots: a structural analysis

Carbon quantum dots (CQDs) have attracted enormous interest in recent years owing to their low cytotoxicity, excellent biocompatibility and strong fluorescence. They have been successfully employed in sensor, bio-imaging, and drug carrier applications. A complete understanding of their core-surface structure is essential for tuning their physical and chemical properties for various applications. Conventional characterizations of CQDs are conducted with electron microscopy or spectroscopy, such as transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. However, these techniques cannot fully resolve the core-surface structure of CQDs. In this study, we attempt to analyze the structures of CQDs by laser desorption/ionization mass spectrometry (LDI-MS) using three model CQDs synthesized from citric acid (CA-CQDs), diammonium citrate (AC-CQDs) and spermidine trihydrochloride (Spd-CQDs). Both CA-CQDs and AC-CQDs produced anionic carbon cluster ions ([C_n]^-, n = 4-9) during the laser desorption/ionization process. Additionally, AC-CQDs produced fragments containing C, N, and O that appeared at m/z values of 41.999, 91.015, and 107.008, which were identified by ¹⁵N isotopes as [CNO]^-, [CH₃N₂O₃]^-, and [CH₃N₂O₄]^-, respectively. By contrast, subjecting Spd-CQDs to the same analysis did not yield carbon cluster ions ([C_n]^-); instead, strong chlorine-associated ions with a unique isotopic pattern were observed, strongly implying that Spd-CQDs contain chlorine. The lack of carbon cluster ion formation in nitrogen- and chlorine-doped Spd-CQDs indicates that nitrogen and chlorine are abundantly and homogenously doped in the CQDs. We also found a shot-dependent fragmentation behavior for AC-CQDs that produces nitrogen- and oxygen-containing ions and carbon cluster ions ([C_n]^-) during initial fragmentation of the surface, with a gradual destruction of the nanocrystalline carbon core after additional shots. These results suggest that LDI-MS can be used as a tool for analyzing the core-surface structure of CQDs, particularly when it contains a heteroatom doped carbon core with various surface functional groups containing nitrogen, oxygen and halogens.