基于G-四联体/血红素形成的DNA酶催化增敏鲁米诺-H2O2发光反应原理,建立了微流控顺序注射化学发光检测K+的新方法。在K+的促进作用下,富含鸟嘌呤的寡核苷酸PS5.M折叠成G-四联体,并对血红素表现出较高的亲合力,形成DNA酶,显著地增强血红素的类辣根过氧化物酶活性,催化鲁米诺-H2O2化学发光反应。在优化的实验条件下,化学发光检测K+的线性范围为1.0~700μmol·L-1,检出限为0.54μmol·L-1,用100μmol·L-1的K+形成的DNA酶连续测定10次,相对标准偏差(RSD)为1.61%。常见的碱金属和碱土金属离子均无显著干扰。该方法可用于真实水样中K+的分析,测定结果与原子吸收法一致。
With the catalysis of K+-mediated G-quadruplex/hemin DNAzyme on the reaction between luminol and hydrogen peroxide,a new microfluidic-based sequential-injection chemiluminescent method was developed for the determination of K+.The G-rich oligonucleotide PS5.M can fold into G-quadruplex induced by K+and bind hemin with high affinity to form DNAzyme.The DNAzyme with horseradish peroxidase-mimicking activity catalyzes luminol and hydrogen peroxide chemiluminescence reaction.Under the optimal conditions,a linear calibration curve(R2=0.991)over the range of 1.0-700μmol·L-1 was obtained with a detection limit of 0.54μmol·L-1.The relative standard deviation for determination of DNAzyme induced by 100μmol·L-1 K+was 1.61%(n=10).Most common alkaline and alkaline earth metal ions had no obvious interference.The developed method was applied for the determination of K+in real water samples and the results were in good agreement with those obtained by atomic absorption spectrometry.