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Functionalized Ag/Fe-MOFs nanocomposite as a novel endogenous redox mediator for determination of α2,6-sialylated glycans in serum

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Abstract

The development of a novel signal amplification system is described for sensitive determination of α2,6-sialylated glycans (α2,6-sial-Gs), an important prognostic tumor biomarker. First, Fe-based metal-organic frameworks (Fe-MOFs) with silver nanoparticles (AgNPs) decorated onto the outer surface were designed and synthesized with controlled octahedron structures. The new Ag/Fe-MOFs nanocomposite possessed strong conductivity and a large surface area to carry more nanoprobes. To connect the Ag/Fe-MOFs nanocomposite with more groups, the nanocomposite was functionalized by -COOH with SH-PEG-COOH to bind with an α2,6-sial-Gs catcher, M-APBA, via -CONH- bonds. More importantly, the Ag/Fe-MOFs also exhibited an excellent endogenous redox mediator property to produce electrons, which is the fundamental mechanism underlying amplification of an electronic signal. A gold electrode was used to accelerate electron transfer and immobilize the α2,6-sial-Gs lectin (SNA). After the sandwich-type catcher recognition (SNA/α2,6-sial-Gs/M-APBA), the current peak response was provoked in the process of oxidizing AgNPs to Ag+ in the forward anodic potential sweep, while Cl− in a PBS solution was transferred into Ag+ to maintain charge neutrality. Optimized particles were employed for direct fabrication of the sandwich-type affinity biosensor, which was found to show a linear detection range from 1 fg mL−1 to 1 ng mL−1 with a detection limit of 0.09 fg mL−1. Furthermore, the biosensor exhibited excellent specificity and stability, indicating that such a novel nanobiotechnology platform can be used to initiate potential utility for monitoring biomarkers in serum.

Graphical abstract

(A)Schematic presentation of synthesis and surface modification of Ag/Fe-MOFs. The new Ag/Fe-MOFs nanocomposite possessed commendable conductivity and large surface area to carry more nanoprobe; after functionalizing the Ag/MOFs with SH-PEG-COOH, the functionalized endogenous redox mediator (c-Ag/MOFs) realized the possibility that can connect with the biological catcher. (B) Schematic diagram of electrode construction for detecting α2,6-sialylated glycans (α2,6-sial-Gs). By using the c-Ag/Fe-MOFs functional endogenous redox mediator, we successfully implemented the electrochemical detection of α2,6-sial-Gs.

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Acknowledgments

We are grateful for the financial support from Chongqing precision medical key technology research and development and demonstration projects (cstc2016shms-ztzx0042).

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Author notes

  1. Yunfei Zhao and Jun Chen contributed equally to this work.

Authors and Affiliations

  1. College of Pharmacy, Chongqing Medical University, Box 380#, 1 Yi Xue Yuan Road, Chongqing, 400016, People’s Republic of China

    Yunfei Zhao, Jun Chen, Yuan Zhou, Weiran Mao & Chao Yu

  2. Chongqing Key Laboratory for Pharmaceutical Metabolism Research, Chongqing, 400016, People’s Republic of China

    Yunfei Zhao, Jun Chen, Yuan Zhou, Weiran Mao & Chao Yu

  3. Chongqing Pharmacodynamic Evaluation Engineering Technology Research Center, Chongqing, 400016, People’s Republic of China

    Yunfei Zhao, Jun Chen, Yuan Zhou, Weiran Mao & Chao Yu

  4. School of Public Health, Chongqing Medical University, Chongqing, 400016, People’s Republic of China

    Hangtian Zhong

  5. ZiGong First People’s Hospital, Zigong, 643000, Sichuan, People’s Republic of China

    Chengli Zhang

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  1. Yunfei Zhao
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  2. Jun Chen
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  4. Chengli Zhang
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Correspondence to Chao Yu.

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Zhao, Y., Chen, J., Zhong, H. et al. Functionalized Ag/Fe-MOFs nanocomposite as a novel endogenous redox mediator for determination of α2,6-sialylated glycans in serum. Microchim Acta 187, 649 (2020). https://doi.org/10.1007/s00604-020-04608-w

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