Feitosa Luís Guilherme Pereira, Feres Juliana Massimino, Godinho Camila Capel, Albernaz Lorena Carneiro, Espindola Laila Salmen, Vessecchi Ricardo, Guaratini Thais, Lopes Norberto Peporine
Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil.
Heborá Ltda, Supera Parque de Inovação e Tecnologia, Ribeirão Preto, SP, Brazil.
Rapid Commun Mass Spectrom. 2025 Apr 30;39(12):e10025. doi: 10.1002/rcm.10025.
Dengue, an arboviral disease transmitted by the Aedes aegypti mosquito, is a major global public health problem challenge. Insecticides based on natural products can provide a good alternative to synthetic agents, as they are safer for both the environment and human health. This study evaluated the activity of geopropolis from stingless bees and Apis mellifera bees on Ae. aegypti, using mass spectrometry approaches to identify compounds with larvicidal potential against Ae. aegypti.
The larvicidal activity of propolis from stingless bees and A. mellifera, as well as the Melipona quadrisfasciata geopropolis (a mixture of soil/clay and propolis), was evaluated against Ae. aegypti larvae (Rockefeller strain). ESI-MS/MS analyses were performed using a quadrupole/time-of-flight mass spectrometer for all geopropolis samples, the geopropolis from Melipona quadrifasciata was also analyzed using an ion trap instrument. The ESI-qTOF-MS/MS data were processed in a spectral similarity network using GNPS. Molecular annotation of potential compounds was performed using the in silico tool called NAP. Gas-phase fragmentation mechanisms were proposed in conjunction with computational chemistry studies. Silylated geopropolis samples were also analyzed by GC-MS.
Geopropolis from the stingless bee M. quadrifasciata caused 90% and 100% mortality in Ae. aegypti larvae after 24 and 48 h of exposure, respectively, exhibiting the highest activity. Mass spectrometry-based molecular network approach supported the suggestion of discriminant compounds between active and inactive samples. The combination of NAP predictions with gas-phase reactions from ESI-MS/MS and EI-MS data facilitated the annotation of larvicidal compounds, including diterpene resin acids, such as dehydroabietic acid and its derivatives, abietic acid, and pimaranes.
The combination of HPLC-MS/MS and GC-MS data suggests that diterpene resin acids contribute to the larvicidal effect of M. quadrifasciata geopropolis on Ae. aegypti, enhancing our understanding of potentially bioactive natural products against the arbovirus vector.
登革热是一种由埃及伊蚊传播的虫媒病毒疾病，是全球主要的公共卫生挑战。基于天然产物的杀虫剂对环境和人类健康都更安全，可为合成药剂提供良好的替代选择。本研究评估了无刺蜂和意大利蜜蜂的地蜂胶对埃及伊蚊的活性，采用质谱方法鉴定具有杀埃及伊蚊幼虫潜力的化合物。
评估了无刺蜂和意大利蜜蜂的蜂胶以及四带无刺蜂地蜂胶（土壤/粘土和蜂胶的混合物）对埃及伊蚊幼虫（洛克菲勒品系）的杀幼虫活性。使用四极杆/飞行时间质谱仪对所有地蜂胶样品进行电喷雾串联质谱（ESI-MS/MS）分析，还使用离子阱仪器对四带无刺蜂的地蜂胶进行了分析。ESI-qTOF-MS/MS数据在使用全球天然产物社会分子网络（GNPS）的光谱相似性网络中进行处理。使用名为NAP的计算机工具对潜在化合物进行分子注释。结合计算化学研究提出了气相裂解机制。还通过气相色谱-质谱联用（GC-MS）分析了硅烷化的地蜂胶样品。
四带无刺蜂的地蜂胶在暴露24小时和48小时后，分别导致埃及伊蚊幼虫90%和100%的死亡率，表现出最高活性。基于质谱的分子网络方法支持了活性和非活性样品之间判别化合物的建议。将NAP预测与ESI-MS/MS和电子电离质谱（EI-MS）数据的气相反应相结合，有助于对杀幼虫化合物进行注释，包括二萜树脂酸，如脱氢枞酸及其衍生物、枞酸和海松烷。
高效液相色谱-串联质谱（HPLC-MS/MS）和GC-MS数据的结合表明，二萜树脂酸有助于四带无刺蜂地蜂胶对埃及伊蚊的杀幼虫作用，增进了我们对针对虫媒病毒载体的潜在生物活性天然产物的理解。
