Xiaofei Li: Pharmacy College, Henan University of Chinese Medicine, Zhengzhou, 450046, PR China.
Yawen Zhang: Pharmacy College, Henan University of Chinese Medicine, Zhengzhou, 450046, PR China.
Lulu Hao: Pharmacy College, Henan University of Chinese Medicine, Zhengzhou, 450046, PR China.
Yanju Liu: Pharmacy College, Henan University of Chinese Medicine, Zhengzhou, 450046, PR China.
Xia Wang: Pharmacy College, Henan University of Chinese Medicine, Zhengzhou, 450046, PR China. Electronic address: wangxiawx83@126.com.
Huaixia Yang: Pharmacy College, Henan University of Chinese Medicine, Zhengzhou, 450046, PR China. Electronic address: yhx998@hactcm.edu.cn.
Jinming Kong: School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing, 210094, PR China. Electronic address: j.kong@njust.edu.cn.
Cytokeratin fragment antigen 21-1 (CYFRA 21-1) DNA is perceived as sensitive tumor marker for the diagnosis of non-small cell lung cancer and other tumor. Herein, linear chain poly(ε-caprolactone) (PCL) synthesized by ring-opening polymerization is applied to ultrasensitive label-free electrochemical impedance detection system for CYFRA 21-1 DNA. First, thiolated peptide nucleic acid (PNA) is self-assembled into the Au electrode surface through the formation of Au-S bonds, allowing the PNA to act as biomolecular probe and form PNA/DNA heteroduplex with the target DNA via specific hybridization. Then, PCL is conjugated to the immobilized DNA on the electrode via "carboxylate-Zr-phosphate" bridges. Finally, the electrochemical response of modified PNA/DNA/Zr/PCL electrode is determined by electrochemical impedance method to quantify of CYFRA 21-1 DNA. Under optimal conditions, this method exhibits highly sensitivity with a broad linear range (0.1 fM - 1 nM) (R = 0.995) and the limit of detection (LOD) is as low as 10.73 aM, which is equivalent to just 64 molecules in a 10 μL sample. What's more, the high selectivity, good anti-interference, label-free operation, and real-time monitoring in complex samples of the proposed strategy demonstrate its broad application for the early diagnosis and clinical monitoring.