Analysis of atorvastatin in environmental waters: Validation of an electrochemical molecularly imprinted polymer sensor with application of life cycle assessment.

The widespread presence of pharmaceuticals in wastewater effluents after treatment stands as a significant challenge faced in the field of wastewater management and public health. Governments and the scientific community have worked to meet this urgent need for effective solutions. Nevertheless, the development of detection strategies for pharmaceutical monitorization capable of delivering rapid, on-site, and sensitive responses remains an ongoing necessity. In this work, the performance of a previously developed molecularly imprinted polymer (MIP) based electrochemical sensor for detecting atorvastatin (ATV) in wastewater effluents and surface waters is presented. A simple preconcentration method followed by electrochemical measurements by differential pulse voltammetry (DPV) in 0.1 M phosphate buffer (pH = 7), was implemented. The analytical results were validated with those obtained on a set of 16 water samples by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Additionally, a life cycle assessment (LCA) was conducted to compare the environmental impact of both methodologies. The results obtained demonstrated that ATV detection using MIP-sensor was reliable when compared to the results found by UHPLC-MS/MS presenting a robust linear correlation coefficient of 0.843. The LCA results show that the novel MIP-sensor technique has lower associated environmental impacts than UHPLC-MS/MS, when the current analytical protocol for pharmaceuticals detection is applied. These findings highlight the potential of the developed MIP-sensor as an eco-friendly analytical tool for routine analysis and point-of-care monitoring of ATV in WWTP wastewater and surface water samples.

Computational Modelling and Sustainable Synthesis of a Highly Selective Electrochemical MIP-Based Sensor for Citalopram Detection.

A novel molecularly imprinted polymer (MIP) has been developed based on a simple and sustainable strategy for the selective determination of citalopram (CTL) using screen-printed carbon electrodes (SPCEs). The MIP layer was prepared by electrochemical in situ polymerization of the 3-amino-4 hydroxybenzoic acid (AHBA) functional monomer and CTL as a template molecule. To simulate the polymerization mixture and predict the most suitable ratio between the template and functional monomer, computational studies, namely molecular dynamics (MD) simulations, were carried out. During the experimental preparation process, essential parameters controlling the performance of the MIP sensor, including CTL:AHBA concentration, number of polymerization cycles, and square wave voltammetry (SWV) frequency were investigated and optimized. The electrochemical characteristics of the prepared MIP sensor were evaluated by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Based on the optimal conditions, a linear electrochemical response of the sensor was obtained by SWV measurements from 0.1 to 1.25 µmol L-1 with a limit of detection (LOD) of 0.162 µmol L-1 (S/N = 3). Moreover, the MIP sensor revealed excellent CTL selectivity against very close analogues, as well as high imprinting factor of 22. Its applicability in spiked river water samples demonstrated its potential for adequate monitoring of CTL. This sensor offers a facile strategy to achieve portability while expressing a willingness to care for the environment.

Electropolymerized, Molecularly Imprinted Polymer on a Screen-Printed Electrode-A Simple, Fast, and Disposable Voltammetric Sensor for Trazodone.

In recent years, analytical chemistry has been facing new challenges, particularly in developing low-cost, green, and easy-to-reproduce methods. In this work, a simple, reproducible, and low-cost electrochemical (voltammetric) molecularly imprinted polymer (MIP) sensor was designed specifically for the detection of trazodone (TZD). Trazodone (TZD) is an antidepressant drug consumed worldwide since the 1970s. By combining electropolymerization (surface imprinting) with screen-printed electrodes (SPCEs), the sensor is easy to prepare, is environmentally friendly (uses small amounts of reagents), and can be used for in situ analysis through integration with small, portable devices. The MIP was obtained using cyclic voltammetry (CV), using 4-aminobenzoic acid (4-ABA) as the functional monomer in the presence of TZF molecules in 0.1 M HCl. Non-imprinted control was also constructed in the absence of TZD. Both polymers were characterized using CV, and TZD detection was performed with DPV using the oxidation of TZD. The polymerization conditions were studied and optimized. Comparing the TZD signal for MIP/SPCE and NIP/SPCE, an imprinting factor of 71 was estimated, indicating successful imprinting of the TZD molecules within the polymeric matrix. The analytical response was linear in the range of 5-80 µM, and an LOD of 1.6 µM was estimated. Selectivity was evaluated by testing the sensor for molecules with a similar structure to TZD, and the ability of MIP/SPCE to selectively bind to TZD was proven. The sensor was applied to spiked tap water samples and human serum with good recoveries and allowed for a fast analysis (around 30 min).

Low Cost, Easy to Prepare and Disposable Electrochemical Molecularly Imprinted Sensor for Diclofenac Detection.

In this work, a disposable electrochemical (voltammetric) molecularly imprinted polymer (MIP) sensor for the selective determination of diclofenac (DCF) was constructed. The proposed MIP-sensor permits fast (30 min) analysis, is cheap, easy to prepare and has the potential to be integrated with portable devices. Due to its simplicity and efficiency, surface imprinting by electropolymerization was used to prepare a MIP on a screen-printed carbon electrode (SPCE). MIP preparation was achieved by cyclic voltammetry (CV), using dopamine (DA) as a monomer in the presence of DCF. The differential pulse voltammetry (DPV) detection of DCF at MIP/SPCE and non-imprinted control sensors (NIP) showed an imprinting factor of 2.5. Several experimental preparation parameters were studied and optimized. CV and electrochemical impedance spectroscopy (EIS) experiments were performed to evaluate the electrode surface modifications. The MIP sensor showed adequate selectivity (in comparison with other drug molecules), intra-day repeatability of 7.5%, inter-day repeatability of 11.5%, a linear range between 0.1 and 10 µM (r2 = 0.9963) and a limit of detection (LOD) and quantification (LOQ) of 70 and 200 nM, respectively. Its applicability was successfully demonstrated by the determination of DCF in spiked water samples (river and tap water).

Molecularly imprinted polymer-based electrochemical sensors for environmental analysis.

The ever-increasing presence of contaminants in environmental waters is an alarming issue, not only because of their harmful effects in the environment but also because of their risk to human health. Pharmaceuticals and pesticides, among other compounds of daily use, such as personal care products or plasticisers, are being released into water bodies. This release mainly occurs through wastewater since the treatments applied in many wastewater treatment plants are not able to completely remove these substances. Therefore, the analysis of these contaminants is essential but this is difficult due to the great variety of contaminating substances. Facing this analytical challenge, electrochemical sensing based on molecularly imprinted polymers (MIPs) has become an interesting field for environmental monitoring. Benefiting from their superior chemical and physical stability, low-cost production, high selectivity and rapid response, MIPs combined with miniaturized electrochemical transducers offer the possibility to detect target analytes in-situ. In most reports, the construction of these sensors include nanomaterials to improve their analytical characteristics, especially their sensitivity. Moreover, these sensors have been successfully applied in real water samples without the need of laborious pre-treatment steps. This review provides a general overview of electrochemical MIP-based sensors that have been reported for the detection of pharmaceuticals, pesticides, heavy metals and other contaminants in water samples in the past decade. Special attention is given to the construction of the sensors, including different functional monomers, sensing platforms and materials employed to achieve the best sensitivity. Additionally, several parameters, such as the limit of detection, the linear concentration range and the type of water samples that were analysed are compiled.

INT reduction is a valid proxy for eukaryotic plankton respiration despite the inherent toxicity of INT and differences in cell wall structure.

The reduction of 2-para (iodophenyl)-3(nitrophenyl)-5(phenyl) tetrazolium chloride (INT) is increasingly being used as an indirect method to measure plankton respiration. Its greater sensitivity and shorter incubation time compared to the standard method of measuring the decrease in dissolved oxygen concentration, allows the determination of total and size-fractionated plankton respiration with higher precision and temporal resolution. However, there are still concerns as to the method's applicability due to the toxicity of INT and the potential differential effect of plankton cell wall composition on the diffusion of INT into the cell, and therefore on the rate of INT reduction. Working with cultures of 5 marine plankton (Thalassiosira pseudonana CCMP1080/5, Emiliania huxleyi RCC1217, Pleurochrysis carterae PLY-406, Scrippsiella sp. RCC1720 and Oxyrrhis marina CCMP1133/5) which have different cell wall compositions (silica frustule, presence/absence of calcite and cellulose plates), we demonstrate that INT does not have a toxic effect on oxygen consumption at short incubation times. There was no difference in the oxygen consumption of a culture to which INT had been added and that of a replicate culture without INT, for periods of time ranging from 1 to 7 hours. For four of the cultures (T. pseudonana CCMP1080/5, P. carterae PLY-406, E. huxleyi RCC1217, and O. marina CCMP1133/5) the log of the rates of dissolved oxygen consumption were linearly related to the log of the rates of INT reduction, and there was no significant difference between the regression lines for each culture (ANCOVA test, F = 1.696, df = 3, p = 0.18). Thus, INT reduction is not affected by the structure of the plankton cell wall and a single INT reduction to oxygen consumption conversion equation is appropriate for this range of eukaryotic plankton. These results further support the use of the INT technique as a valid proxy for marine plankton respiration.