Polysaccharides are complex but essential compounds utilized in many areas such as biomaterials, drug delivery, cosmetics, food chemistry or renewable energy. Modifications and functionalizations of such polymers are often necessary to achieve molecular structures of interest. In this area, the emergence of the “click” chemistry concept, and particularly the copper-catalyzed version of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides, had an impact on the polysaccharides chemistry. The present review summarizes the contribution of “click” chemistry in the world of polysaccharides.
There is a global debate and concern about the use of glyphosate (Gly) as an herbicide. New toxicological studies will determine its use in the future under new strict conditions or its replacement by alternative synthetic or natural herbicides. In this context, we designed biomimetic polymer sensing layers for the selective molecular recognition of Gly. Towards this end, complementary surface acoustic wave (SAW) and electrochemical sensors were functionalized with polypyrrole (PPy)-imprinted polymer for the selective detection of Gly. Their corresponding limits of detection were on the order of 1 pM, which are among the lowest values ever reported in literature. The relevant dissociation constants between PPy and Gly were estimated at [Kd1 = (0.7 ± 0.3) pM and Kd2 = (1.6 ± 1.4) µM] and [Kd1 = (2.4 ± 0.9) pM and Kd2 = (0.3 ± 0.1) µM] for electrochemical and gravimetric measurements, respectively. Quantum chemical calculations permitted to estimate the interaction energy between Gly and PPy film: ΔE = −145 kJ/mol. Selectivity and competitivity tests were investigated with the most common pesticides. This work conclusively shows that gravimetric and electrochemical results indicate that both MIP-based sensors are perfectly able to detect and distinguish glyphosate without any ambiguity.
A shear horizontal surface acoustic wave sensor (SH-SAW) operating at 104 MHz was functionalized with a polypyrrole (PPy) molecularly imprinted polymer (MIP) for selective detection of flumequine (FLU) in aqueous media. In order to prevent the formation of FLU complexes with the gold sensing area of the SH-SAW sensor, a thin blocking polypyrrole layer was deposited by chronoamperometry before the MIP electrochemical deposition. The detection limit of the designed sensor was of the order of 1 μM and the sensitivity was estimated to be at 9.36 ± 0.39° mM−1. Selectivity tests were made with levofloxacin (LEVO), an interfering fluoroquinolone antibiotic. Results indicate that the designed PPy-MIP recognition layer is selective of flumequine. Quantum chemical calculations, based on density functional theory (DFT), have permitted us to highlight the importance of the PPy blocking layer, on the one hand, and the nature of interactions between the polypyrrole matrix and FLU and LEVO analytes, on the other hand.
This review critically summarizes the knowledge of imprinted polymer-based electrochemical sensors for the detection of pesticides, metal ions and waterborne pathogenic bacteria, focusing on the last five years. MIP-based electrochemical sensors exhibit low limits of detection (LOD), high selectivity, high sensitivity and low cost. We put the emphasis on the design of imprinted polymers and their composites and coatings by radical polymerization, oxidative polymerization of conjugated monomers or sol-gel chemistry. Whilst most imprinted polymers are used in conjunction with differential pulse or square wave voltammetry for sensing organics and metal ions, electrochemical impedance spectroscopy (EIS) appears as the chief technique for detecting bacteria or their corresponding proteins. Interestingly, bacteria could also be probed via their quorum sensing signaling molecules or flagella proteins. If much has been developed in the past decade with glassy carbon or gold electrodes, it is clear that carbon paste electrodes of imprinted polymers are more and more investigated due to their versatility. Shortlisted case studies were critically reviewed and discussed; clearly, a plethora of tricky strategies of designing selective electrochemical sensors are offered to “Imprinters”. We anticipate that this review will be of interest to experts and newcomers in the field who are paying time and effort combining electrochemical sensors with MIP technology.
p-Toluenesulfonyl cellulose was prepared by reacting cellulose in aqueous medium, instead of via traditional routes, which involve the use of DMAc/LiCl, or more recently, ionic liquids. The influence of several parameters on the reaction efficiency has been studied; amount of tosylchloride, presence of triethylamine, reaction time and use of sodium hydroxide or sodium chloride. The resulting p-toluenesulfonyl cellulose samples were characterized by means of FTIR and NMR spectroscopy. The effects of solvent on the crystalline change during tosylation were investigated by X-ray diffraction (XRD). The degree of substitution (DS) was determined by 1H NMR and confirmed by X-ray photoelectron spectroscopy (XPS). Tosylcelluloses with DS from 0.1 to 1.7 have been prepared.