Enabling Multiplexed Electrochemical Detection of Biomarkers with High Sensitivity in Complex Biological Samples

Acc Chem Res. 2021 Sep 21;54(18):3529-3539. doi: 10.1021/acs.accounts.1c00382. Epub 2021 Sep 3.

Abstract

The ability to perform multiplexed detection of various biomarkers within complex biological fluids in a robust, rapid, sensitive, and cost-effective manner could transform clinical diagnostics and enable personalized healthcare. Electrochemical (EC) sensor technology has been explored as a way to address this challenge because it does not require optical instrumentation and it is readily compatible with both integrated circuit and microfluidic technologies; yet this approach has had little impact as a viable commercial bioanalytical tool to date. The most critical limitation hindering their clinical application is the fact that EC sensors undergo rapid biofouling when exposed to complex biological samples (e.g., blood, plasma, saliva, urine), leading to the loss of sensitivity and selectivity. Thus, to break through this barrier, we must solve this biofouling problem.In response to this challenge, our group has developed a rapid, robust, and low-cost nanocomposite-based antifouling coating for multiplexed EC sensors that enables unprecedented performance in terms of biomarker signal detection compared to reported literature. The bioinspired antifouling coating that we developed is a nanoporous composite that contains various conductive nanomaterials, including gold nanowires (AuNWs), carbon nanotubes (CNTs), or reduced graphene oxide nanoflakes (rGOx). Each study has progressively evolved this technology to provide increasing performance while simplifying process flow, reducing time, and decreasing cost. For example, after successfully developing a semipermeable nanocomposite coating containing AuNWs cross-linked to bovine serum albumin (BSA) using glutaraldehyde, we replaced the nanomaterials with reduced graphene oxide, reducing the cost by 100-fold while maintaining similar signal transduction and antifouling properties. We, subsequently, developed a localized heat-induced coating method that significantly improved the efficiency of the drop-casting coating process and occurs within the unprecedented time of <1 min (at least 3 orders of magnitude faster than state-of-the-art). Moreover, the resulting coated electrodes can be stored at room temperature for at least 5 months and still maintain full sensitivity and specificity. Importantly, this improved coating showed excellent antifouling activity against various biological fluids, including plasma, serum, whole blood, urine, and saliva.To enable affinity-based sensing of multiple biomarkers simultaneously, we have developed multiplexed EC sensors coated with the improved nanocomposite coating and then employed a sandwich enzyme-linked immunosorbent assay (ELISA) format for signal detection in which the substrate for the enzyme bound to the secondary antibody precipitates locally at the molecular binding site above the electrode surface. Using this improved EC sensor platform, we demonstrated ultrasensitive detection of a wide range of biomarkers from biological fluids, including clinical biomarkers, in both single and multiplex formats (N = 4) with assay times of 37 and 15 min when integrated with a microfluidic system. These biosensors developed demonstrate the vast potential of solving the biofouling problem, and how it can enable potential clinically important diagnostic applications. This Account reviews our antifouling surface chemistry and the multiplexed EC sensor-based biodetection method we developed and places it in context of the various innovative contributions that have been made by other researchers in this field. We are optimistic that future iterations of these systems will change the way diagnostic testing is done, and where it can be carried out, in the future.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Antibodies / analysis
  • Biofouling / prevention & control
  • Biomarkers / analysis*
  • Body Fluids / chemistry
  • Body Fluids / metabolism
  • Electrochemical Techniques / methods*
  • Enzyme-Linked Immunosorbent Assay
  • Humans
  • Microfluidics
  • Nanocomposites / chemistry
  • Point-of-Care Systems

Substances

  • Antibodies
  • Biomarkers