Nunes Nádia, Popović Iva, Abreu Elder, Maciel Dina, Rodrigues João, Soto Juan, Algarra Manuel, Petković Marijana
CQM-Centro de Química da Madeira, Universidade da Madeira, Campus da Penteada, 9020-105, Funchal, Portugal.
Department of Atomic Physics, VINČA Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia.
Talanta. 2021 Jan 15;222:121551. doi: 10.1016/j.talanta.2020.121551. Epub 2020 Aug 25.
We studied the possibility of detection of [Ru(η-CH)(PPh)Cl] (abbreviated by RuCp) complex as a model system for Ru-based metallodrugs in human urine by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) without previous purification or removal of inorganic salts. Inorganic salts might prevent the detection of RuCp by MALDI-TOF MS, most likely through the increased number and intensity of background/organic matrix signals. This problem might be overcome by the acquisition of matrix-free spectra and the addition of nanoparticles, such as carbon dots, to the urine solution. Our results suggest that RuCp is easily detectable by MALDI-TOF MS in all acquisition conditions, with the CHCA matrix being the best for acquisition in phosphate-containing solutions, whereas in urine, DHB and matrix-free approach demonstrated the highest sensitivity, precision, and reproducibility. The sensitivity of matrix-free MALDI detection of RuCp could be increased by the addition of carbon dots to the urine. Based on theoretical calculations for all matrix/analyte combinations, the model for the interaction of RuCp with carbon dots was established, and higher sensitivity explained.
我们研究了使用基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF MS）在不预先纯化或去除无机盐的情况下，检测[Ru(η-CH)(PPh)Cl]（简称为RuCp）配合物作为基于钌的金属药物在人尿中的模型系统的可能性。无机盐可能会阻止通过MALDI-TOF MS检测RuCp，最有可能是通过增加背景/有机基质信号的数量和强度。通过采集无基质光谱以及向尿液溶液中添加纳米颗粒（如碳点），这个问题可能会得到克服。我们的结果表明，在所有采集条件下，RuCp都能通过MALDI-TOF MS轻松检测到，CHCA基质最适合在含磷酸盐的溶液中采集，而在尿液中，DHB和无基质方法表现出最高的灵敏度、精密度和重现性。通过向尿液中添加碳点，可以提高RuCp的无基质MALDI检测灵敏度。基于对所有基质/分析物组合的理论计算，建立了RuCp与碳点相互作用的模型，并解释了更高的灵敏度。
