Developing imprinted polymer nanoparticles for the selective separation of antidiabetic drugs.

In this study, new molecularly imprinted polymer (MIP) nanoparticles are designed for selective recognition of different drugs used for the treatment of type 2 diabetes mellitus, i.e. sitagliptin (SG) and metformin (MF). The SG- and MF-imprinted polymer nanoparticles are synthesized by free-radical initiated polymerization of the functional monomers: methacrylic acid and methyl methacrylate; and the crosslinker: ethylene glycol dimethacrylate. The surface morphology of resultant MIP nanoparticles is studied by atomic force microscopy. Fourier transform infrared spectra of MIP nanoparticles suggest the presence of reversible, non-covalent interactions between the template and the polymer. The effect of pH on the rebinding of antidiabetic drugs with SG- and MF-imprinted polymers is investigated to determine the optimal experimental conditions. The molecular recognition characteristics of SG- and MF-imprinted polymers for the respective drug targets are determined at low concentrations of SG (50-150 ppm) and MF (5-100 ppm). In both cases, the MIP nanoparticles exhibit higher binding response compared to non-imprinted polymers. Furthermore, the MIPs demonstrate high selectivity with four fold higher responses toward imprinted drugs targets, respectively. Recycled MIP nanoparticles retain 90% of their drug-binding efficiency, which makes them suitable for successive analyses with significantly preserved recognition features.

Thermodynamic, chemical, and electrochemical studies of Aloe ferox Mill extract as a naturally developing copper corrosion inhibitor in HCl solution.

Copper can be susceptible to corrosion in acidic cleaning solutions for desalination system, especially if the solution is highly concentrated or if the cleaning process involves extended exposure to the acid. In the current work, Aloe ferox Mill (AFM extract) can be used as a natural origin corrosion inhibitor for copper in 1.0 M HCl solution. The corrosion mitigation qualities of AFM extract were assessed by means of electrochemical, gravimetric, and surface examinations. AFM extract is a mixed-type inhibitor, based on polarization research findings. The inhibitory effectiveness of AFM extract rises with concentration, reaching its maximum level (93.3%) at 250 mg L-1. The inclusion of AFM extract raises the activation energy for the corrosion reaction from 7.15 kJ mol-1 (blank solution) to 28.6 kJ mol-1 (at 250 mg L-1 AFM extract).

Determination of sitagliptin in human plasma using a smart electrochemical sensor based on electroactive molecularly imprinted nanoparticles.

Sitagliptin is a hypoglycaemic agent used to reduce blood sugar levels in patients with type 2 diabetes mellitus (T2DM). Real time monitoring of sitagliptin levels is crucial to prevent overdose, which might cause liver, kidney and pancreatic diseases. As an alternative solution, a sitagliptin voltammetric sensor was fabricated using artificial receptors called electroactive molecularly imprinted polymer nanoparticles (nanoMIPs). The nanoMIP tagged with a redox probe (ferrocene) combines both the recognition and reporting functions. Traditional electrochemical sensors determine the redox activity of an analyte. Thus, they are influenced by interfering molecules and the nature of the sample. These innovative nanoMIPs allow us to easily design and customise sensors, increase their sensitivity and minimise the cross reactivity in biological samples. The present technology replaces the traditional enzyme-mediator pairs used in traditional biosensors. The polymer composition was optimized "in silico" using docking and screening methods. Nanoparticles were synthesized via free radical polymerization and a solid phase method and then characterized by infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and dynamic light scattering (DLS). The specific sitagliptin nanoparticles were covalently immobilized on platinum electrodes via silane and carbodiimide chemistry. The determination of sitagliptin in human plasma by a nanoMIP sensor was assessed by differential pulse voltammetry (DPV). The sensor current response was directly related to the change in nanoMIP conformation triggered by the analyte. The optimisation of the sensor response was made by adjusting (i) the silane concentration, (ii) nanoMIP concentration, and (iii) immobilization time. The sensor measurements in plasma revealed high selectivity and a sensitivity of 32.5 ± 0.6 nA pM-1 towards sitagliptin, and the limit of detection of the fabricated sensor was found to be 0.06 pM. The sensor displayed a satisfactory performance for the determination of sitagliptin in spiked human plasma, demonstrating the potential of this technology for drug monitoring and clinical diagnosis.

Design and fabrication of a smart sensor using in silico epitope mapping and electro-responsive imprinted polymer nanoparticles for determination of insulin levels in human plasma.

A robust and highly specific sensor based on electroactive molecularly imprinted polymer nanoparticles (nanoMIP) was developed. The nanoMIP tagged with a redox probe, combines both recognition and reporting capabilities. The developed nanoMIP replaces enzyme-mediator pairs used in traditional biosensors thus, offering enhanced molecular recognition for insulin, improving performance in complex biological samples, and yielding high stability. Also, most of existing sensors show poor performance after storage. To improve costs of the logistics and avoid the need of cold storage in the chain supply, we developed an alternative to biorecognition system that relies on nanoMIP. NanoMIP were computationally designed using "in-silico" insulin epitope mapping and synthesized by solid phase polymerisation. The characterisation of the polymer nanoparticles was performed by transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier-transform Infrared (FT-IR) and surface plasmon resonance (SPR). The electrochemical sensor was developed by chemical immobilisation of the nanoMIP on screen printed platinum electrodes. The insulin sensor displayed satisfactory performances and reproducible results (RSD = 4.2%; n = 30) using differential pulse voltammetry (DPV) in the clinically relevant concentration range from 50 to 2000 pM. The developed nanoMIP offers the advantage of large number of specific recognition sites with tailored geometry, as the resultant, the sensor showed high sensitivity and selectivity to insulin with a limit of detection (LOD) of 26 and 81 fM in buffer and human plasma, respectively, confirming the practical application for point of care monitoring. Moreover, the nanoMIP showed adequate storage stability of 168 days, demonstrating the robustness of sensor for several rounds of insulin analysis.