A Sensitive Approach on Trace Analysis of Methylparaben in Wastewater and Cosmetic Products Using Molecularly Imprinted Polymer

Parabens are the antimicrobial molecules largely used in cosmetic products as a preservative agent. Among them, the methylparaben (MP) is the most frequently used ingredient in cosmetic preparations. Nevertheless, their potential dangers led to the development of sensible and reliable methods for their determination in environmental samples. Firstly, a sensitive and selective molecular imprinted polymer (MIP) based on screen-printed gold electrode (Au-SPE), assembled on a polymeric layer of carboxylated poly(vinyl-chloride) (PVC-COOH), was developed. After the template removal, the obtained material was able to rebind MP and discriminate it among other interfering species such as glucose, sucrose, and citric acid. The behavior of molecular imprinted sensor was characterized by Cyclic Voltammetry (CV), Differential Pulse Voltammetry (DPV) and Electrochemical Impedance Spectroscopy (EIS) techniques. Then, the biosensor was found to have a linear detection range from 0.1 pg.mL-1 to 1 ng.mL-1 and a low limit of detection of 0.12 fg.mL-1 and 5.18 pg.mL-1 by DPV and EIS, respectively. For applications, this biosensor was employed to determine MP content in four wastewaters in Meknes city and two cosmetic products (shower gel and shampoo). The operational reproducibility and stability of this biosensor were also studied. Secondly, another MIP biosensor based on tungsten trioxide (WO3) functionalized by gold nanoparticles (Au-NPs) assembled on a polymeric layer of PVC-COOH was developed. The main goal was to increase the sensitivity of the biosensor. The developed MIP biosensor was successfully applied for the MP determination in wastewater samples and cosmetic products.

Synthesis of Highly Sensitive Molecular Imprinted Sensor for Selective Determination of Doxycycline in Honey Samples

Doxycycline (DXy) is a cycline antibiotic, most frequently prescribed to treat bacterial infections in veterinary medicine. However, its broad antimicrobial activity and low cost, lead to an intensive use, which can seriously affect human health. Therefore, its spread in the food products has to be monitored. The scope of this work was to synthetize a sensitive and very selective molecularly imprinted polymer (MIP) for DXy detection in honey samples. Firstly, the synthesis of this biosensor was performed by casting a layer of carboxylate polyvinyl chloride (PVC-COOH) on the working surface of a gold screen-printed electrode (Au-SPE) in order to bind covalently the analyte under mild conditions. Secondly, DXy as a template molecule was bounded to the activated carboxylic groups, and the formation of MIP was performed by a biocompatible polymer by the mean of polyacrylamide matrix. Then, DXy was detected by measurements of differential pulse voltammetry (DPV). A non-imprinted polymer (NIP) prepared in the same conditions and without the use of template molecule was also performed. We have noticed that the elaborated biosensor exhibits a high sensitivity and a linear behavior between the regenerated current and the logarithmic concentrations of DXy from 0.1 pg.mL−1 to 1000 pg.mL−1. This technic was successfully applied to determine DXy residues in honey samples with a limit of detection (LOD) of 0.1 pg.mL−1 and an excellent selectivity when compared to the results of oxytetracycline (OXy) as analogous interfering compound. The proposed method is cheap, sensitive, selective, simple, and is applied successfully to detect DXy in honey with the recoveries of 87% and 95%. Considering these advantages, this system provides a further perspective for food quality control in industrial fields.

Development of Molecular Imprinted Polymers (MIPs) for the Selective Removal of Carbamazepine from Aqueous Solution

The occurrence and removal of trace organic contaminants in the aquatic environment has become a focus of environmental concern. For the selective removal of carbamazepine from loaded waters molecularly imprinted polymers (MIPs) were synthesized with carbamazepine as template. Parameters varied were the type of monomer, crosslinker, and porogen, the ratio of starting materials, and the synthesis temperature. Best results were obtained with a template to crosslinker ratio of 1:20, toluene as porogen, and methacrylic acid (MAA) as monomer. MIPs were then capable to recover carbamazepine by 93% from a 10-5 M landfill leachate solution containing also caffeine and salicylic acid. By comparison, carbamazepine recoveries of 75% were achieved using a nonimprinted polymer (NIP) synthesized under the same conditions, but without template. In landfill leachate containing solutions carbamazepine was adsorbed by 93-96% compared with an uptake of 73% by activated carbon. The best solvent for desorption was acetonitrile, with which the amount of solvent necessary and dilution with water was tested. Selected MIPs were tested for their reusability and showed good results for at least five cycles. Adsorption isotherms were prepared with carbamazepine solutions in the concentration range of 0.01 M to 5*10-6 M. The heterogeneity index showed a more homogenous binding site distribution.