纳米纤维在线固相萃取检测尿液中3种儿茶酚胺和5-羟色胺  

Determination of three urinary catecholamines and serotonin by on-line packed-fiber solid-phase extraction

作　　者：毕月玲 许桐 陈利琴[2,3] BI Yueling;XU Tong;CHEN Liqin(Department of Pharmacy, Tianjin Xiqing Hospital, Tianjin 300380, China;Department of Toxicology and Sanitary Chemistry, School of Public Health, Tianjin Medical University, Tianjin 300070, China;Tianjin Key Laboratory of Environment, Nutrition and Public Health, Tianjin 300070, China)

机构地区：[1]天津市西青医院药剂科,天津300380 [2]天津医科大学公共卫生学院卫生毒理与卫生化学教研室,天津300070 [3]天津市环境营养与人群健康重点实验室,天津300070

出　　处：《色谱》2021年第12期1306-1313,共8页Chinese Journal of Chromatography

基　　金：西青医院科联体项目(XQYYKLT202004).

摘　　要：生物单胺包括儿茶酚胺类以及5-羟色胺等,在中枢神经系统中扮演着非常关键的角色,也是临床上诊断神经内分泌肿瘤疾病的重要生物标志物。由于这类单胺类物质的强化学极性导致传统吸附材料对其吸附效果不佳,从复杂生物样本中同时检测更多的生物单胺存在挑战性。该文建立了一种基于聚冠醚纳米纤维在线固相萃取检测尿液中3种儿茶酚胺(多巴胺、肾上腺素、去甲肾上腺素)和5-羟色胺的方法。采用静电纺丝法制备聚二苯并-18-冠-6醚-聚苯乙烯复合纳米纤维(PCE-PS),制成装填纤维的固相萃取(PFSPE)柱,再将PFSPE柱与HPLC进行在线联用。该在线PFSPE-HPLC方法采用双三元泵进行样品富集净化和分析,左泵连接PFSPE柱,进行样品富集净化;右泵连接分析柱进行样品分离检测。控制切换阀的切换,实现样品富集后洗脱至分析柱中分离检测。结果表明,在线PFSPE-HPLC检测尿液儿茶酚胺(多巴胺、肾上腺素、去甲肾上腺素)和5-羟色胺在1~200 ng/mL范围内有良好的线性关系,线性相关系数达0.996以上。3种儿茶酚胺和5-羟色胺的检出限(S/N=3)分别为1和2.5 ng/mL,定量限(S/N=10)分别为2.5和5 ng/mL。空白尿液和实际尿液加标回收率在83.5%~117.7%之间,日内精密度<10%。PCE-PS复合纳米纤维在多次使用后无明显变化,具有良好的稳定性,可重复使用达95次以上。在线PFSPE-HPLC方法能够集样品在线前处理与分析检测于一体,省时省力,实现分析过程的高度自动化。该方法成功应用于尿液中3种儿茶酚胺和5-羟色胺的检测,可以为临床上相关疾病检测诊断和研究提供有力的技术支持。Biogenic monoamines,including catecholamines(CAs)and serotonin(5-HT),play critical roles in the central nervous system.They have recently been proven to be primarily useful as biomarkers for the diagnosis of CA-producing tumors.The highly polar properties of biogenic monoamines result in poor retention on conventional materials,making it challenging to simultaneously measure more biogenic monoamines from complex matrices.Moreover,the classical method of off-line pretreatment is relatively complex,labor-intensive,and incurs errors in repeatability among different operators.Therefore,the development of an on-line sample pretreatment method combined with the use of specific nanofiber adsorbents has been explored.An on-line procedure could avoid unnecessary and time-consuming steps,and enable full automation of the experimental process.In this study,an on-line packed-fiber solid-phase extraction(PFSPE)and determination method for urinary CAs(dopamine(DA),norepinephrine(NE),epinephrine(E))and 5-HT was developed,using composite nanofibers of polycrown ether-polystyrene(PCE-PS).PCE-PS composite nanofibers prepared by electrospinning were used as adsorbents in the PFSPE column,which was connected to the on-line HPLC system.The PFSPE-HPLC equipment contained a dual ternary pump and a switching valve to enable enrichment,purification,and analysis directly in the system.The left pump was connected with the PFSPE column for sample enrichment and purification,while the right pump was attached to the analysis column for sample separation and testing.The switching valve was controlled such that after enrichment,the samples could be eluted to the analysis column for separation and detection.The current work expands on our previous research by analyzing more target substances,and developing an on-line sample pretreatment method to simultaneously analyze four biogenic monoamines.Gradient separation aided in the satisfactory separation of the biogenic monoamines within a short retention time.The running time was set at 16 min to en

关 键 词：聚冠醚复合纳米纤维 高效液相色谱 在线固相萃取 儿茶酚胺 5-羟色胺 尿 

分 类 号：O658[理学—分析化学]