Elsevier

Biosensors and Bioelectronics

Volume 100, 15 February 2018, Pages 56-70
Biosensors and Bioelectronics

Recent advances and future prospects in molecularly imprinted polymers-based electrochemical biosensors

https://doi.org/10.1016/j.bios.2017.08.058Get rights and content

Highlights

  • This review paper systematically summarizes the recent advances of MIPs-based ECBSs.

  • The sensing applications of MIPs-based ECBSs for various important biomolecules are addressed.

  • The present challenges and further prospects of MIPs-based ECBSs are also highlighted.

Abstract

Molecularly imprinted polymers (MIPs)-based electrochemical biosensors (ECBSs) have many advantages from MIPs and ECBSs, such as high selectivity and sensitivity, chemical/mechanical stability, reusability, low limit of detection, facile preparation and low cost. MIPs-based ECBSs attract much attention in medical diagnose, biological analysis, environmental monitoring, food safety evaluation, etc. Due to the capacity of highly specific recognition for target biomolecules, MIPs-based ECBSs have been smartly designed and extensively used for electrochemical sensing applications in recent years, exhibiting obvious superiority over other analytical techniques. In this review, firstly we systematically summarize the recent advances of MIPs-based ECBSs reported in recent years, referring to the preparation, structures and components of sensing systems. Secondly, we highlight the sensing applications for various significant biomolecules (proteins, antibiotics, pesticide, neurotransmitter, hormone, etc.), and demonstrate the sensing mechanism and detection performance. Finally, the rational summaries, present challenges and future prospects in the field of MIPs-based ECBSs have been discussed reasonably.

Introduction

Molecularly imprinted polymers (MIPs) have attracted much attention due to unique properties, such as simplicity, low cost, facile preparation, high selectivity and sensitivity. Usually, typical MIPs include template molecules, functional monomers, cross-linking reagents, etc. Functional monomers interact with templates through non-covalent (hydrogen bond, ionic or hydrophobic) and covalent interactions to form a complex before cross-linking reaction in solvent. A general procedure for MIPs synthesis involves: 1) template molecules combine with the assembly of functional monomers to fabricate a complex via covalent or non-covalent bonds in solution; 2) cross-linkers and initiators polymerize with the complex under photo-/thermal conditions; 3) the removal of embedded templates in polymers through extraction often uses solvent elution because the analyte has a higher solubility in the solvent. Microcavities with a three dimensional structure complementary in the shape and chemical functionality to templates are generated after template removal. MIPs containing microcavities have excellent capabilities for specifically and sensitively rebinding targets with the near shape and microstructure of templates (Okutucu and Önal, 2011, Xu et al., 2013).

Synthesis of MIPs mainly involves the bulk, multi-step swelling, suspension and precipitation polymerizations. To give artificial recognition functions, complementary microcavities are created for specific targets, like the “key-and-lock” (Chen et al., 2011). As biomimetic synthetic receptors, MIPs have specific cavities for targets, superior to natural antibody recognition. MIPs recognition is mechanically and chemically stable even at an extreme pH and temperature, suitable for MIPs preparation and reusability. When templates are produced from polymers at the molecular level, MIPs can recognize and rebind targets with high specificity and affinity, much superior to natural receptors. Due to these characteristics, MIPs play an important role in environmental, clinical and food fields. Especially, MIPs have been explored in the field of Analytical Chemistry: stationary phases for HPLC (Moein et al., 2011, Jin et al., 2013), capillary electrochromatography (Huang et al., 2011), enzyme-linked sorbents for chemiluminescence (Jing et al., 2011), colorimetric assay (Rossetti et al., 2014), etc. As functionalized polymers, MIPs with specific recognition for targets are very suitable for fabricating electrochemical biosensors (Scheme 1).

MIPs-based electrochemical biosensors (ECBSs) have the advantages from MIPs and ECBSs, including high selectivity and sensitivity, chemical/mechanical stability, reusability, low limit of detection (LOD), facile preparation, low cost, miniaturization and automation (Blanco-López et al., 2004). Thus, MIPs-based ECBSs attract much attention in medical diagnosis, biological analysis, environmental monitoring and food safety evaluation (Tong et al., 2013, Xue et al., 2013, Yang et al., 2013). MIPs-based ECBSs have been widely used for the analysis of important biomolecules, such as proteins, hormones, drugs, nucleic acids, etc. (Guan et al., 2008, Suriyanarayanan et al., 2012). The highly mechanical/thermal stability, excellent specificity and sensitivity of MIPs-based ECBSs for targets indicate a greater prospect for high-quality sensing applications, over traditional instrument techniques and other types of sensors.

Before this review, we have searched for other reviews relative to MIPs-based ECBSs in Web of Science. A review on MIPs-based electrochemical sensors was published previously (Piletsky and Turner, 2002). Moreno-Bondi et al. (2008) reviewed MIPs as the selective recognition elements in optical sensing. Suriyanarayanan et al. (2010) reported a review on molecularly imprinted electrochemical sensors. Whitcombe et al. (2011) reviewed the rational development of MIPs-based sensors for proteins detection. Most recently, Yola and Atar (2017) published a review on the recent developments of molecularly imprinted electrochemical sensors based on carbon nanomaterials. Yanez-Sedeno et al. (2017) reported a review on electrochemical sensors based on magnetic MIPs. Previous reviews referred to MIPs or MIPs-based sensors, but some reviews were published for a long time interval. The recent reviews involved carbon nanomaterials-based molecularly imprinted electrochemical sensors and magnetic MIPs-based electrochemical sensors. Previous reviews are not enough to provide a comprehensive review on MIPs and MIPs-based sensors. During the past decade, great publications have been dedicated to MIPs-based ECBSs due to unique advantages from MIPs and ECBSs. The MIPs-based ECBSs have been widely designed for electrochemical analysis, showing obvious superiority over other analytical techniques. However, so far a timely and overall review is still lacking about the important topic of MIPs-based ECBSs. This present review overall summarizes the recent advances of MIPs-based ECBSs reported in recent years, and highlights the sensing applications for various important biomolecules. The present challenges and further prospects of MIPs-based ECBSs are also discussed.

Section snippets

A brief introduction of MIPs-based ECBSs

The MIPs-based ECBSs involving molecular imprinting techniques and electrochemical sensors have the superiority for selective and sensitive sensing of targets. The sensors use MIPs as specific recognition elements for templates and serve as smart devices for electrochemical signal output. The integration of MIPs and electrochemical devices is promising for developing biosensors (Luo et al., 2013). High specificity for targets and detection capability are two key requirements for effective

Sensing applications of MIPs-based ECBSs

In recent years, important studies have referred to MIPs-based ECBSs that exhibit significant applications for biomolecule sensing. Based on superior sensing performance over other analytical techniques, currently MIPs-based ECBSs are widely used for highly selective sensing of important biomolecules, referring to proteins, antibiotics, pesticide, neurotransmitter, hormone, etc. In this section, we overall summarize the recent advances of MIPs-based ECBSs for sensing applications of various

Conclusions and prospects

MIPs have many advantages, including simplicity, low cost and facile preparation. The internal microcavities endow MIPs excellent capability for specifically rebinding target molecules with the same shape and microstructure as template molecules, like “key-and-lock”. After combination of MIPs with the surface of electrodes modified with electroactive materials, MIPs-based sensors can be fabricated for specifically recognizing and electrochemically sensing targets. Recognition and sensing of

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (21475071 and 21405086), the Taishan Scholar Program of Shandong (ts201511027), the Natural Science Foundation of Shandong (ZR2014BQ001 and ZR2016BB37), and the Source Innovation Plan Application Basic Research Project of Qingdao (17-1-1-72-jch).

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