Zhang Suling, Liu Hengli, Li Xiaoyang, Yao Weixuan, Ying Jianbo, Lü Ting, Zhang Dong, Zhao Hongting, Pan Ying
College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou, China.
Department of Criminal Science and Technology, Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province, Zhejiang Police College, Hangzhou, China.
J Sep Sci. 2025 Jul;48(7):e70221. doi: 10.1002/jssc.70221.
A facile dispersive micro-solid phase extraction (D-μ-SPE) method that uses spherical cellulose aerogels is proposed herein for the trace detection of seven benzodiazepines in biological samples. Zirconium metal-organic framework (MOF) particles were dispersed in the cellulose aerogels to improve the extraction efficiency. The prepared lightweight spherical aerogels (diameter of approximately 2 mm) were easily collected from the solution using a disposable dropper, overcoming the difficult recycling of powdered MOFs. The effect of the MOF loading (39, 56, and 66 wt%) and the organic ligand (terephthalic acid, 2-aminoterephthalic acid, and 4,4'-biphenyldicarboxylic acid) in the Zr-MOF on the extraction ability of the hybrid aerogels towards benzodiazepines was studied. The hybrid aerogel with a UiO-67 loading of 66% showed the best extraction performance primarily because of the enhanced surface area, pore volume, and π-π stacking interactions. Moreover, the UiO-67/cellulose aerogel spheres were mechanically stable and showed reusability for at least eight consecutive extraction cycles. The main factors affecting extraction, such as solution pH, extraction time, type and volume of desorption solvent, and desorption time, were also examined. Under the optimal conditions, the limits of detection ranged from 0.01 to 0.03 µg/L, and the limits of quantification ranged from 0.02 to 0.10 µg/L. The recoveries were 81.8%-104.2% for urine samples and 81.5%-99.5% for hair samples. The results suggest that the spherical aerogel-based D-μ-SPE is a simple and effective method for the quantification of benzodiazepines in biological samples.
本文提出了一种使用球形纤维素气凝胶的简便分散微固相萃取（D-μ-SPE）方法，用于生物样品中七种苯二氮䓬类药物的痕量检测。将锆基金属有机框架（MOF）颗粒分散在纤维素气凝胶中以提高萃取效率。制备的轻质球形气凝胶（直径约2毫米）使用一次性滴管即可轻松从溶液中收集，克服了粉末状MOF回收困难的问题。研究了Zr-MOF中MOF负载量（39%、56%和66%重量）和有机配体（对苯二甲酸、2-氨基对苯二甲酸和4,4'-联苯二甲酸）对混合气凝胶对苯二氮䓬类药物萃取能力的影响。负载量为66%的UiO-67混合气凝胶表现出最佳的萃取性能，主要是因为其表面积、孔体积和π-π堆积相互作用增强。此外，UiO-67/纤维素气凝胶球在机械上稳定，并且至少连续八个萃取循环都具有可重复使用性。还考察了影响萃取的主要因素，如溶液pH值、萃取时间、解吸溶剂的类型和体积以及解吸时间。在最佳条件下，检测限为0.01至0.03μg/L，定量限为0.02至0.10μg/L。尿液样品的回收率为81.8%-104.2%，毛发样品的回收率为81.5%-99.5%。结果表明，基于球形气凝胶的D-μ-SPE是一种用于生物样品中苯二氮䓬类药物定量分析的简单有效的方法。
