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Molecularly Imprinted Polymers for Chemical Sensing: a Tutorial Review

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Molecularly Imprinted Polymers for Chemical Sensing: a Tutorial Review chemosensors Review Molecularly Imprinted Polymers for Chemical Sensing: A Tutorial Review Nadja Leibl 1,2, Karsten Haupt 1, Carlo Gonzato 1,* and Luminita Duma 1,* 1 CNRS Enzyme and Cell Engineering Laboratory, Université de Technologie de Compiègne, Sorbonne Universités, Rue du Docteur Schweitzer, CS 60319, CEDEX, 60203 Compiègne, France; [email protected] (N.L.); [email protected] (K.H.) 2 APSYS—An Airbus Company, ZI de Couperigne CTMA Bat B, 13127 Vitrolles, France * Correspondence: [email protected] (C.G.); [email protected] (L.D.) Abstract: The field of molecularly imprinted polymer (MIP)-based chemosensors has been experi- encing constant growth for several decades. Since the beginning, their continuous development has been driven by the need for simple devices with optimum selectivity for the detection of various compounds in fields such as medical diagnosis, environmental and industrial monitoring, food and toxicological analysis, and, more recently, the detection of traces of explosives or their precursors. This review presents an overview of the main research efforts made so far for the development of MIP-based chemosensors, critically discusses the pros and cons, and gives perspectives for further developments in this field. Keywords: molecularly imprinted polymers; chemosensors; sensors Citation: Leibl, N.; Haupt, K.; Gonzato, C.; Duma, L. Molecularly 1. Introduction Imprinted Polymers for Chemical Molecularly imprinted polymers (MIPs) have seen a continuous development as Sensing: A Tutorial Review. sensing elements in bio-/chemo-sensors since the late 1990s [1–6]. MIPs are attractive Chemosensors 2021, 9, 123. not only for their recognition properties that are close to those of natural receptors and https://doi.org/10.3390/ their availability for a wide range of targets but also for their superior chemical and chemosensors9060123 physical stability compared to biological receptors. These advantages have led to the application of MIPs in fields as various as immunoassays, separation, depollution, sensing, Academic Editor: Chung-Wei Kung cell imaging, and therapy [7–9]. The imprinting process consists of polymerizing functional and cross-linking monomers in the presence of a template. The removal of the later leaves Received: 14 April 2021 cavities complementary in shape, size, and chemical functionality, therefore allowing for Accepted: 20 May 2021 the template to rebind specifically. Published: 26 May 2021 According to the International Union of Pure and Applied Chemistry (IUPAC), a chemical sensor is “a device that transforms chemical information, ranging from the con- Publisher’s Note: MDPI stays neutral centration of a specific sample component to total composition analysis, into an analytically with regard to jurisdictional claims in useful signal. The chemical information, mentioned above, may originate from a chemical published maps and institutional affil- reaction of the analyte or from a physical property of the system investigated” [10]. There- iations. fore, a suitable sensor has to fulfil specific criteria such as high sensitivity and selectivity, stability, low sample consumption, reliability, and reproducibility. Overall, an ideal sensor should also be inexpensive, portable, foolproof, able to instantaneously respond to the analyte of interest in any desired medium, and capable of generating a measurable signal Copyright: © 2021 by the authors. in the required concentration range. Unfortunately, current sensors are far from being Licensee MDPI, Basel, Switzerland. “ideal”, and chemical sensors in particular are generally narrowly optimized for a given This article is an open access article application [11,12]. distributed under the terms and As mentioned above, a chemical sensor consists of two main elements (see Scheme1): conditions of the Creative Commons the chemical recognition element, called the receptor, and a physico-chemical transducer. Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ The receptor transforms the binding event of the target into a form of energy that can be 4.0/). measured by the transducer. For chemical sensors, this binding event involves chemical Chemosensors 2021, 9, 123. https://doi.org/10.3390/chemosensors9060123 https://www.mdpi.com/journal/chemosensors Chemosensors 2021, 9, x FOR PEER REVIEW 2 of 19 Chemosensors 2021, 9, 123 2 of 19 can be measured by the transducer. For chemical sensors, this binding event involves chemicalspecies and species the generationand the generation of a signal of upon a sign theal changeupon the of change a physico-chemical of a physico-chemical parameter parameter(e.g., the formation/breaking (e.g., the formation/breaking of a bond, of exchange a bond, exchange of electrons, of electrons, and mass and change mass or change refrac- ortive refractive index modification). index modification). Subsequently, Subsequent the transducerly, the transducer transforms transforms the chemical the information chemical received from the receptor into a useful analytical signal. The transduction process can be information received from the receptor into a useful analytical signal. The transduction based on several physical phenomena, such as optical or thermal changes, electrochemical process can be based on several physical phenomena, such as optical or thermal changes, reactions, and mass variations. electrochemical reactions, and mass variations. SchemeScheme 1. 1. SchemeScheme of a chemical sensor sensor consisting consisting of of arecognition a recognition layer, layer, an interface, an interface, a transducer, a transducer, and a signaland a detectionsignal detection element. element. As a recent trend, the miniaturization of sensors and their readout deserves a special attentionAs a recent due to trend, the increasing the miniaturization number of of applications sensors and available their readout for smartphones deserves a special [13–17]. attentionFrom a general due to the point increasing of view, number receptor of design applications is perhaps available the crucial for smartphones step in the [13–17]. process Fromof sensor a general development point of view, because receptor it has design to match is perhaps the requirements the crucial of step high in selectivitythe process and of sensorsensitivity development for a target because with it the has particular to match characteristicsthe requirements of aof given high selectivity readout. Thus,and sen- the sitivitystraightforward for a target engineering, with the particular fine-tuning, characteristics and easiness of a given of integration readout. Thus, into thethe standardstraight- forwardindustrial engineering, process of MIPsfine-tuning, makes and them easiness ideal candidates of integration for recognition into the standard elements. industrial processIn of this MIPs review, makes we them describe ideal the candidates current state for recognition of the research elements. field on MIP-based elec- trochemical,In this review, mass-sensitive, we describe and the optical current sensors, state of and the we research highlight field their on MIP-based advantages elec- and trochemical,shortcomings. mass-sensitive, The last section and discussesoptical sensors, aspects and related we highlight to chemical their interfacing advantages in and the shortcomings.design of MIP-based The last chemosensors. section discusses Reviews aspect froms related 2020 and to chemical 2021 already interfacing described in the various de- signcharacteristics of MIP-based related chemosensors. to MIP synthesis Reviews and from the 2020 readout and 2021 mode already of MIP-based described potentio- various characteristicsmetric sensors related for the to detection MIP synthesis of organic and andthe biologicalreadout mode species of MIP-based [18], the advantages potentiom- of etricnanomaterial-based sensors for the MIPsdetection for pesticidesof organic sensing and biological [19], and species the strength/weakness [18], the advantages ratio forof nanomaterial-basedpotentiometric sensors MIPs in for general pesticides [20], which sensing are [19], not and tackled the instrength/weakness this work. ratio for potentiometric sensors in general [20], which are not tackled in this work. 2. Electrochemical MIP Sensors 2. ElectrochemicalElectrochemical MIP sensors Sensors represent one of the most successfully applied MIP-based sensorsElectrochemical [21–25]. Electrochemical sensors represent sensors one are of defined the most as devices successfully wherein applied a sensing MIP-based layer is sensorscoupled [21–25]. to an electrochemical Electrochemica transducerl sensors are [26 defined]. Depending as devices on thewherein electrical a sensing phenomenon layer is coupledused for to transducing an electrochemical the binding transducer event, different [26]. Depending families of on electrochemical the electrical sensorsphenomenon can be useddistinguished: for transducing potentiometric the binding (sensing event, a differ changeent in families the membrane of electrochemical potential), conductomet- sensors can beric distinguished: (conductance variation),potentiometric impedimetric (sensing a (impedance change in the fluctuation), membrane and potential), voltammetric conduc- or amperometric (overall current variation induced either by an electrochemical reaction upon tometric (conductance variation), impedimetric (impedance fluctuation), and voltammet- a voltage switch or a time-dependent evolution over a constant potential, respectively) [27]. Chemosensors 2021, 9, x FOR PEER
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