Fabrication of a Selective and Sensitive Sensor Based on Molecularly Imprinted Polymer/Acetylene Black for the Determination of Azithromycin in Pharmaceuticals and Biological Samples.
ABSTRACT: A new selective and sensitive sensor based on molecularly imprinted polymer/acetylene black (MIP/AB) was developed for the determination of azithromycin (AZM) in pharmaceuticals and biological samples. The MIP of AZM was synthesized by precipitation polymerization. MIP and AB were then respectively introduced as selective and sensitive elements for the preparation of MIP/AB-modified carbon paste (MIP/ABP) electrode. The performance of the obtained sensor was estimated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Compared with non-molecularly imprinted polymer (NIP) electrodes, NIP/ABP electrodes, and MIP-modified carbon paste electrodes, MIP/ABP electrode exhibited excellent current response toward AZM. The prepared sensor also exhibited good selectivity for AZM in comparison with structurally similar compounds. The effect of electrode composition, extraction parameters, and electrolyte conditions on the current response of the sensor was investigated. Under the optimized conditions, the prepared sensor showed two dynamic linear ranges of 1.0 × 10-7 mol L-1 to 2.0 × 10-6 mol L-1 and 2.0 × 10-6 mol L-1 to 2.0 × 10-5 mol L-1, with a limit of detection of 1.1 × 10-8 mol L-1. These predominant properties ensured that the sensor exhibits excellent reliability for detecting AZM in pharmaceuticals and biological fluids without the assistance of any separation techniques. The results were validated by the high-performance liquid chromatography-tandem mass spectrometry method.
Project description:A simple, efficient and reliable analytical method was developed and used for the determination of the fluvoxamine drug (FLV) in pharmaceutical preparations and biological fluids. The method is based on the cost-effective screen-printed platform for the potential transduction of the drug. Host-tailored molecular imprinting polymer (MIP) was integrated with the potentiometric platform as a recognition receptor, in which FLV, acrylamide (AAm), ethylene glycol dimethacrylate (EGDMA) and acetonitrile were used as a template, functional monomer, cross-linker, and solvent, respectively. MIP particles were dispersed in plasticized poly (vinyl chloride) (PVC) and the membrane was drop-casted on carbon screen-printed electrode. The MIP, in addition to non-imprinted polymers (NIP), was characterized and the binding experiment revealed high affinity and adsorption capacity of MIP towards FLV. The proposed sensor displayed near-Nernstian cationic slope of 55.0 ± 0.8 mV/decade (r2 = 0.999) with a low detection limit of 4.8 × 10-6 mol/L over a wide pH range (3.0-8.5). The electrochemical features of the proposed sensors including electrochemical impedance spectroscopy (EIS) and chronopotentiometry measurements (CP) in the presence of multi-walled carbon nanotubes (MWCNTs) as a solid contact transducer were also investigated. The applications of the proposed sensor for the determination of FLV in different dosage forms with recovery values (98.8%-101.9%) and (97.4%-101.1%), respectively compared with the reference HPLC method with acceptedFandt-student tests values at the 95% confidence level.
Project description:In this study, a new electrochemical sensor was developed for the detection of cefalexin (CFX), based on the use of a molecularly imprinted polymer (MIP) obtained by electro‒polymerization in an aqueous medium of indole-3-acetic acid (I3AA) on a glassy carbon electrode (GCE) and on boron-doped diamond electrode (BDDE). The two different electrodes were used in order to assess how their structural differences and the difference in the potential applied during electrogeneration of the MIP translate to the performances of the MIP sensor. The quantification of CFX was performed by using the electrochemical signal of a redox probe before and after the rebinding of the template. The modified electrode was characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The influence of different parameters on the fabrication of the sensor was tested, and the optimized method presented high selectivity and sensitivity. The MIP-based electrode presented a linear response for CFX concentration range of 10 to 1000 nM, and a limit of detection of 3.2 nM and 4.9 nM was obtained for the BDDE and the GCE, respectively. The activity of the sensor was successfully tested in the presence of some other cephalosporins and of other pharmaceutical compounds. The developed method was successfully applied to the detection of cefalexin from real environmental and pharmaceutical samples.
Project description:An origami three-dimensional design of a paper-based potentiometric sensor is described. In its simplest form, this electrochemical paper-based analytical device (ePAD) is made from three small parts of the paper. Paper layers are folded on each other for the integration of a solid contact ion selective electrode (here a carbon-paste composite electrode) and a solid-state pseudo-reference electrode (here writing pencil 6B on the paper), which are in contact with a hydrophilic channel fabricated on the middle part (third part) of the paper. In this case, the pseudo-reference and working electrodes are connected to the two sides of the hydrophilic channel and hence the distance between them is as low as the width of paper. The unmodified carbon paste electrode (UCPE) and modification with the crown ether benzo15-crown-5 (B15C5) represented a very high sensitivity to Cu (II) and Cd<sup>2+</sup> ions, respectively. The sensor responded to H<sub>2</sub>O<sub>2</sub> using MnO<sub>2</sub>-doped carbon paste electrode (CPE). Furthermore, a biosensor was achieved by the addition of glucose oxidase to the MnO<sub>2</sub>-doped CPE and hence made it selective to glucose with ultra-sensitivity. In addition to very high sensitivity, our device benefits from consuming a very low volume of sample (10.0 µL) and automatic sampling without need for sampling devices.
Project description:The heart is a fundamental organ of the human circulatory system and the continuous measurement of electrocardiogram (ECG) signals is of great importance for pre-detection of heart diseases. Dry electrodes that do not require electrolyte gel have been developed for wearable ECG monitoring applications. However, this kind of electrode often introduces motion artifacts because of the high contact impedance between the electrode and skin. We propose a wearable ECG monitoring garment that employs electrodes made of conductive carbon-based paste. This paste is directly applied to the skin and after drying for 5 min, it forms a patch electrode that is detachable and flexible. The contact impedance between the patch electrode and the skin is very low because the paste covers the skin in a conformal manner. The experimental results show that the contact area of the carbon-based paste on the skin replica is almost 100%. At frequencies under 10 Hz, the contact impedance of the patch electrode is of 70.0 k?, much lower than the typical 118.7 k? impedance of a Ag/AgCl electrode. We also demonstrate that the ECG signals measured using the custom-designed garment and the patch electrodes are very stable even during actions such as walking and running.
Project description:Trimethylamine N-oxide (TMAO), a microbiota-derived metabolite has been implicated in human health and disease. Its early detection in body fluids has been presumed to be significant in understanding the pathogenesis and treatment of many diseases. Hence, the development of reliable and rapid technologies for TMAO detection may augment our understanding of pathogenesis and diagnosis of diseases that TMAO has implicated. The present work is the first report on the development of a molecularly imprinted polymer (MIP) based electrochemical sensor for sensitive and selective detection of TMAO in body fluids. The MIP developed was based on the polypyrrole (PPy), which was synthesized via chemical oxidation polymerization method, with and without the presence of TMAO. The MIP, NIP and the non-sonicated polymer (PPy-TMAO) were separately deposited electrophoretically onto the hydrolyzed indium tin oxide (ITO) coated glasses. The chemical, morphological, and electrochemical behavior of MIP, non-imprinted polymer (NIP), and PPy-TMAO were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and electrochemical techniques. The detection response was recorded using differential pulse voltammetry (DPV), which revealed a decrease in the peak current with the increase in concentration of TMAO. The MIP sensor showed a dynamic detection range of 1-15 ppm with a sensitivity of 2.47 µA mL ppm<sup>-1</sup> cm<sup>-2</sup>. The developed sensor is easy to construct and operate and is also highly selective to detect TMAO in body fluids such as urine. The present research provides a basis for innovative strategies to develop sensors based on MIP to detect other metabolites derived from gut microbiota that are implicated in human health and diseases.
Project description:A new modified glassy carbon electrode (GCE) based on a synthesized N-(2-aminoethyl)-4,4'-bipyridine (ABP) was developed for the determination of Ag(I) by differential pulse voltammetry (DPV). ABP was covalently immobilized on GC electrodes surface using 4-nitrobenzendiazonium (4-NBD) and glutaraldehyde (GA). The Ag(I) ions were preconcentrated by chemical interaction with bipyridine under a negative potential (-0.6 V); then the reduced ions were oxidized by differential pulse voltammetry and a peak was observed at 0.34 V. The calibration curve was linear in the concentration range from 0.05 ?M to 1 ?M Ag(I) with a detection limit of 0.025 ?M and RSD=3.6%, for 0.4 ?M Ag(I). The presence of several common ions in more than 125-fold excess had no effect on the determination of Ag(I). The developed sensor was applied to the determination of Ag(I) in water samples using a standard addition method.
Project description:There is a growing interest in the technological transfer of highly performing electrochemical sensors within portable analytical devices for the in situ monitoring of environmental contaminants, such as perfluorooctanesulfonic acid (PFOS). In the redesign of biomimetic sensors, many parameters should be taken into account from the working conditions to the electrode surface roughness. A complete characterization of the surface modifiers can help to avoid time-consuming optimizations and better interpret the sensor responses. In the present study, a molecularly imprinted polymer electrochemical sensor (MIP) for PFOS optimized on gold disk electrodes was redesigned on commercial gold screen-printed electrodes. However, its performance investigated by differential pulse voltammetry was found to be poor. Before proceeding with further optimization, a morphological study of the bare and modified electrode surfaces was carried out by scanning electron microscopy-energy-dispersive X-ray spectrometry (SEM-EDS), atomic force microscopy (AFM) and profilometry revealing an heterogeneous distribution of the polymer strongly influenced by the electrode roughness. The high content of fluorine of the target-template molecule allowed to map the distribution of the molecularly imprinted polymer before the template removal and to define a characterization protocol. This case study shows the importance of a multi-analytical characterization approach and identify significant parameters to be considered in similar redesigning studies.
Project description:Electrochemical nanosensors based on nanoporous gold leaf (NPGL) and molecularly imprinted polymer (MIP) are developed for pharmaceutical analysis by using metronidazole (MNZ) as a model analyte. NPGL, serving as the loading platform for MIP immobilization, possesses large accessible surface area with superb electric conductivity, while electrochemically synthesized MIP thin layer affords selectivity for specific recognition of MNZ molecules. For MNZ determination, the hybrid electrode shows two dynamic linear range of 5 × 10(-11) to 1 × 10(-9) mol L(-1) and 1 × 10(-9) to 1.4 × 10(-6) mol L(-1) with a remarkably low detection limit of 1.8 × 10(-11) mol L(-1) (S/N = 3). In addition, the sensor exhibits high binding affinity and selectivity towards MNZ with excellent reproducibility and stability. Finally, the reliability of MIP-NPGL for MNZ detection is proved in real fish tissue samples, demonstrating the potential for the proposed electrochemical sensors in monitoring drug and biological samples.
Project description:Determination of an antihyperlipidemic drug simvastatin (SIM) was carried out using a carbon paste electrode bulk-modified with multiwalled carbon nanotubes (MWCNT-CPE). Scanning electrochemical microscopy (SECM), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used for the characterization of the prepared electrodes. Different electrodes were prepared varying in mass percentage of MWCNTs to find out the optimum amount of MWCNTs in the paste. The MWCNT-CPE in which the mass percentage of MWCNTs was 25% (w/w) was found as the optimum. Then, the prepared electrode was used in a mechanistic study and sensitive assay of SIM in pharmaceutical dosage form and a spiked human plasma sample using differential pulse voltammetry (DPV). The prepared electrode shows better sensitivity compared to the bare carbon paste and glassy carbon electrode (GCE). The detection limit and the limit of quantification were calculated to be 2.4 × 10-7 and 8 × 10-7, respectively. The reproducibility of the electrode was confirmed by the low value of the relative standard deviation (RSD% = 4.8%) when eight measurements of the same sample were carried out. Determination of SIM in pharmaceutical dosage form was successfully performed with a bias of 0.3% and relative recovery rate of 99.7%. Furthermore, the human plasma as a more complicated matrix was spiked with a known concentration of SIM and the spiking recovery rate was determined with the developed method to be 99.5%.
Project description:In this paper, a tryptophan (Trp) molecularly imprinted chitosan film was prepared on the surface of an acetylene black paste electrode using chitosan as the functional polymer, Trp as the template molecule and sulfuric acid as the crosslinking agent. The surface morphologies of non-imprinted and imprinted electrodes were characterized by scanning electron microscopy (SEM). The formation of hydrogen bonds between the functional polymer and the template molecule was confirmed by infrared spectroscopy. Some factors affecting the performance of the imprinted electrode such as the concentration of chitosan, the mass ratio of chitosan to Trp, the dropping amount of the chitosan-Trp mixture, the solution pH, and the accumulation potential and time were discussed. The experimental results show that the imprinted electrode exhibit good affinity and selectivity for Trp. The dynamic linear ranges of 0.01-4 M, 4-20 M and 20-100 M were obtained by second derivative linear sweep voltammetry, and the detection limit was calculated to be 8.0 nM. The use of the imprinted electrode provides an effective method for eliminating the interference of potentially interfering substances. In addition, the sensor has high sensitivity, reproducibility and stability, and can be used for the determination of Trp in pharmaceutical preparations and human serum samples.