羟基自由基响应聚集的磁弛豫开关传感器检测伏马毒素B1OA
Hydroxyl Radical Responsive Aggregation Magnetic Relaxation Switch Sensor for Detection of Fumonisin B1
针对伏马毒素B1(FB1)定量检测中面临复杂基质干扰及假阳性等问题,构建了基于超小氧化钆纳米探针及其羟基自由基(·OH)响应性聚集的新型磁弛豫开关(MRSw)传感器,用于特异性高灵敏检测粮食基质中的FB1.采用高温热解法制备了平均粒径约为1.30 nm的Gd2O3-OA纳米颗粒,并经两亲性配体(十二烯基丁二酸酐-酪胺偶联复合物,DDSA-Ty)修饰,获得酪胺功能化的亲水性Gd2O3-Ty NPs顺磁探针.在Fe3O4磁珠表面构建的竞争免疫体系中,目标物FB1 调控辣根过氧化物酶(HRP)的捕获量(以酶标二抗形式HRP-Ab2);磁分离后,上清液中的酶(HRP-Ab2)催化过氧化氢原位生成·OH,通过活化探针表面的酪胺酚羟基进而偶联诱导探针(Gd2O3-Ty NPs)迅速发生特异性共价聚集,显著缩短了体系水质子横向弛豫时间(T2).在优化条件下,横向弛豫时间变化值(ΔT2)与FB1 浓度在10~1000 ng/mL范围内呈良好的线性关系(r=0.992),检出限(LOD)低至3.04 ng/mL.黄曲霉毒素B1 和赭曲霉毒素A等常见共存真菌毒素不干扰检测.将本方法应用于实际小麦粉及玉米粉样品中FB1 的检测,加标回收率为91.0%~103.1%,相对标准偏差(RSD)≤6.9%,检测结果与酶联免疫吸附法(ELISA)结果一致性良好.本研究制备的Gd-MRSw传感器抗基质干扰能力强、操作简便、快速,为复杂食品样本中真菌毒素的精准定量检测提供了新策略.
To address the issues of complex matrix interference and false positives in the quantitative detection of fumonisin B1(FB1),a novel magnetic relaxation switch(MRSw)sensor based on ultra-small gadolinium oxide(Gd2O3)nanoprobes and their hydroxyl radical(·OH)-responsive aggregation was developed for highly sensitive and specific detection of FB1 in food matrices.Hydrophobic Gd2O3-OA nanoparticles with an average particle size of approximately 1.30 nm were synthesized by high-temperature pyrolysis and then phase-transferred with an amphiphilic ligand(Dodecenyl succinic anhydride-tyramine conjugate,DDSA-Ty)to obtain hydrophilic Gd2O3-Ty paramagnetic nanoprobes functionalized with tyramine.In the competitive immunoassay system constructed on the surface of magnetic beads,the target FB1 regulated the capture amount of horseradish peroxidase(In the form of enzyme-labeled secondary antibody,HRP-Ab2).After magnetic separation,the enzyme(HRP-Ab2)in the supernatant catalyzed the in-situ generation of·OH from hydrogen peroxide,which activated the tyramine phenolic hydroxyl groups on the probe surface and induced rapid specific covalent aggregation of the nanoprobes,significantly shortening the transverse relaxation time(T2)of the surrounding water protons.Under optimized conditions,ΔT2 exhibited a good linear relationship with FB1 concentration in the range of 10‒1000 ng/mL(r=0.992),with a limit of detection(LOD)as low as 3.04 ng/mL.This method showed no significant cross-reaction toward commonly coexisting mycotoxins such as aflatoxin B1 and ochratoxin A.The proposed method was applied to detection of actual wheat flour and corn flour samples,yielding spiked recoveries ranging from 91.0%to 103.1%,with relative standard deviation(RSD)≤6.9%,and the detection results were consistent with those of the enzyme-linked immunosorbent assay(ELISA).This Gd-MRSw sensor had strong resistance to matrix interference,and was easy to operate,providing a new strategy for accurate quantitative detection of mycotoxins in complex food samples and holding substantial potential for practical applications.
郭可悦;杜雯鹃;李梁雨;胡高飞;汪乐余
北京化工大学化学学院,化工资源有效利用全国重点实验室,北京 100029北京化工大学化学学院,化工资源有效利用全国重点实验室,北京 100029北京化工大学化学学院,化工资源有效利用全国重点实验室,北京 100029北京化工大学化学学院,化工资源有效利用全国重点实验室,北京 100029北京化工大学化学学院,化工资源有效利用全国重点实验室,北京 100029
磁弛豫开关传感器食品安全伏马毒素B1羟基自由基氧化钆纳米颗粒
Magnetic relaxation switch sensorFood safetyFumonisin B1Hydroxyl radicalGadolinium oxide nanoparticles
《分析化学》 2026 (8)
1346-1355,中插1-中插3,13
国家自然科学基金项目(No.22076010)资助. Supported by the National Natural Science Foundation of China(No.22076010).
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