汞具有高生物毒性,可经水源、土壤污染药食同源食品,危害人体健康。该研究构建了一种基于杂交链式反应(hybridization chain reaction,HCR)的电化学传感检测法,并用于荷叶、金银花、白芷、鱼腥草4种药食同源食品中Hg2+的测定。以金磁纳米粒子固定识别探针,Hg2+通过形成T-Hg2+-T结构与cDNA竞争识别探针。HCR体系由cDNA链和2个发卡探针组成,cDNA与金磁识别探针杂交,暴露触发HCR序列,引发HCR反应,形成含二茂铁(ferrocene,Fc)的dsDNA长链,产生电流信号。结果显示,最优条件下用差分脉冲伏安法(differential pulse voltammetry,DPV)测定Hg2+引起的Fc电流变化(ΔI),其线性方程为ΔI(μA)=0.434 5+0.143 1 lgC (ng/mL),R2=0.994 0,检测限为0.01 ng/mL。对荷叶等4种药食同源样品中的Hg2+进行测定,加标回收率为95.28%~104.77%。该方法灵敏度高、特异性强,在药食同源食品检测中应用前景广阔。
Mercury, a highly toxic heavy metal, can contaminate medicinal and food homologous substances in water and soil, posing significant risks to human health.In this study, an electrochemical sensor based on hybridization chain reaction (HCR) was developed for the detection of Hg2+ in four medicinal and food homologous substances, namely lotus leaf, Lonicera japonica, Angelica dahurica, and Houttuynia cordata Thunb.Gold magnetic nanoparticles were used to immobilize the recognition probes.Hg2+ competed with cDNA for the recognition probe by forming a stable T-Hg2+-T complex.The HCR system consisted of a cDNA strand and two hairpin probes.When cDNA hybridized with the recognition probe on gold magnetic nanoparticles, the sequence that triggers HCR was exposed, initiating a cascade reaction that generated long dsDNA chains.These dsDNA were functionalized with ferrocene (Fc), which could produce a measurable signal.Under optimized conditions, differential pulse voltammetry (DPV) was used to quantify the change in Fc current (ΔI) caused by Hg2+.The linear equation was ΔI(μA)=0.434 5+0.143 1 lgC (ng/mL), with a high coefficient of determination (R2=0.994 0).The detection limit was 0.01 ng/mL.Validation using four representative samples yielded spiked recovery rates ranging from 95.28% to 104.77%.This method has high sensitivity and strong anti-interference ability, and holds great promise for analyzing complex matrices of medicinal and food homologous substances.
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