Sensing by Molecularly Imprinted Polymer: Evaluation of the Binding Properties with Different Techniques.

The possibility of investigating the binding properties of the same molecularly imprinted polymer (MIP), most probably heterogeneous, at various concentration levels by different methods such as batch equilibration and sensing, is examined, considering two kinds of sensors, based respectively on electrochemical and surface plasmon resonance (SPR) transduction. As a proof of principle, the considered MIP was obtained by non-covalent molecular imprinting of 2-furaldehyde (2-FAL). It has been found that different concentration ranges of 2-FAL in aqueous matrices can be measured by the two sensing methods. The SPR sensor responds in a concentration range from 1 × 10-4 M down to about 1 × 10-7 M, while the electrochemical sensor from about 5 × 10-6 M up to about 9 × 10-3 M. The binding isotherms have been fit to the Langmuir adsorption model, in order to evaluate the association constant. Three kinds of sites with different affinity for 2-FAL have been detected. The sites at low affinity are similar to the interaction sites of the corresponding NIP since they have a similar association constant. This is near to the affinity evaluated by batch equilibration too. The same association constant has been evaluated in the same concentration range. The sensing methods have been demonstrated to be very convenient for the characterization of the binding properties of MIP in comparison to the batch equilibration, in terms of reproducibility and low amount of material required for the investigation.

Monitoring of low levels of furfural in power transformer oil with a sensor system based on a POF-MIP platform.

In this work an innovative, miniaturized and low cost optical chemical sensor (POF-MIP platform), based on a molecular imprinted polymer (MIP) and surface plasmon resonance in a plastic optical fiber (POF), is presented and preliminarily tested for monitoring of furfural (furan-2-carbaldehyde) in transformer oil. To this end, the optical platform was coupled to an MIP layer, highly selective for furfural. The ability of the developed sensor to directly detect furfural in the insulating oil was investigated. The detection limit of the sensor has been found to be 9 ppb, with a linear response up to about 30 ppb. However there is a sensible response up to 0.15 ppm. Because of the small linearity range, the Hill equation is suggested for the quantification. The sensor has been effectively tested in real oil samples collected from aged electrical equipment removed from service. The assessed concentration of furfural is in good agreement with that evaluated by a high pressure liquid chromatography (HLPC) method, confirming the good selectivity of the proposed sensor.

An Optical Fiber Sensor for Uranium Detection in Water.

An optical sensor for uranyl has been prepared based on a gold-plated D-shaped plastic optical fiber (POF) combined with a receptor consisting of a bifunctional synthetic molecule, 11-mercaptoundecylphosphonic acid (MUPA), with a phosphonic group for complexing the considered ion, and a sulfide moiety through which the molecule is fixed at the gold resonant surface as a molecular layer in an easy and reproducible way. The sensor is characterized by evaluating the response in function of the uranyl concentration in aqueous solutions of different compositions and real-life samples, such as tap water and seawater. The mechanism of the uranyl/MUPA interaction was investigated. Two different kinds of interactions of uranyl with the MUPA layer on gold from water are observed: a strong one and a weak one. In the presence of competing metal ions as Ca2+ and Mg2+, only the strong interaction takes place, with a high affinity constant (around 107 M-1), while a somewhat lower constant (i.e., around 106 M-1) is obtained in the presence of Mg2+ which forms stronger complexes with MUPA than Ca2+. Due to the high affinity and the good selectivity of the recognition element MUPA, a detection limit of a few µg L-1 is reached directly in natural water samples without any time-consuming sample pretreatment, making it possible for rapid, in situ controls of uranyl by the proposed sensor.

SPR-Optical Fiber-Molecularly Imprinted Polymer Sensor for the Detection of Furfural in Wine.

A surface plasmon resonance (SPR) platform, based on a D-shaped plastic optical fiber (POF), combined with a biomimetic receptor, i.e., a molecularly imprinted polymer (MIP), is proposed to detect furfural (2-furaldheide, 2-FAL) in fermented beverages like wine. MIPs have been demonstrated to be a very convenient biomimetic receptor in the proposed sensing device, being easy and rapid to develop, suitable for on-site determinations at low concentrations, and cheap. Moreover, the MIP film thickness can be changed to modulate the sensing parameters. The possibility of performing single drop measurements is a further favorable aspect for practical applications. For example, the use of an SPR-MIP sensor for the analysis of 2-FAL in a real life matrix such as wine is proposed, obtaining a low detection limit of 0.004 mg L-1. The determination of 2-FAL in fermented beverages is becoming a crucial task, mainly for the effects of the furanic compounds on the flavor of food and their toxic and carcinogenic effect on human beings.