RESUMEN
Stereochemical configuration of the drug is responsible for racemic switch with enantiomers in presence of chiral environment for human beings. Therefore, its determination in racemic and pharmaceutical samples becomes a challenge. Addressing this issue, an enantioselective electrochemical biomimetic sensor for discrimination of isomers of ethambutol (ETB) employing square wave voltammetry (SWV) is reported for the first time. For this purpose, a chiral host, ß-Cyclodextrin based copper metal organic framework (CD-CuMOF) was synthesized and used for chelate complexation of ETB isomers (SS-ETB/RR-ETB). A glassy carbon electrode (GCE) is chemically modified using CD-CuMOF and carbon nanofibers (CNF) composite material to construct a sensor in the form of (CD-CuMOF-CNF-GCE). The behaviour of CD-CuMOF for ETB isomers on GCE is postulated to be an artificial enzyme model (AEM) as it mimics the catalytic activity similar to enzyme alcohol dehydrogenase for ETB. The biosensor exhibits excellent peak potential difference (ΔEp (SS-RR) = 108 mV) between ETB isomers using SWV showing a clear distinction in the racemic mixture. It showed a linear response in the range of 1.0 x 10-7 to 1 x 10-4 M and 5.0 x 10-7 to 2.5 x 10-4 M with low detection limit of 3.10 x 10-8 M and 8.52 x 10-8 M for RR-ETB and SS-ETB isomers respectively. The sensor was applied for the estimation of ETB isomers in racemic mixture and real samples viz., blood, urine and pharmaceutical. The CD-CuMOF is a low-cost material with higher stability than enzyme and offers an advantage for sensing and catalysis in future.
Asunto(s)
Técnicas Biosensibles , Estructuras Metalorgánicas , Nanofibras , beta-Ciclodextrinas , Biomimética , Carbono , Cobre , Técnicas Electroquímicas , Electrodos , Etambutol , HumanosRESUMEN
An electrochemical method based on potentiometric stripping analysis (PSA) employing a hexathia 18C6 (HT18C6) and rice husk (RH) modified carbon paste electrode (HT18C6-RH-CPE) has been proposed for the subnanomolar determination of antimony. The characterization of the electrode surface has been carried out by means of scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and chronocoulometry. By employing HT18C6-RH-CPE, a 12-fold enhancement in the PSA signal (dt/dE) was observed as compared to plain carbon paste electrode (PCPE). Under the optimized conditions, dt/dE (sV(-1)) was proportional to the Sb(III) concentration in the range of 1.42×10(-8) to 6.89×10(-11)M (r=0.9944) with the detection limit (S/N=3) of 2.11×10(-11)M. The practical analytical utilities of the modified electrode were demonstrated by the determination of antimony in pharmaceutical formulations, human hair, sea water, urine and blood serum samples. The prepared modified electrode showed several advantages, such as simple preparation method, high sensitivity, very low detection limit and excellent reproducibility. Moreover, the results obtained for antimony analysis in commercial and real samples using HT18C6-RH-CPE and those obtained by inductively coupled plasma-atomic emission spectrometry (ICP-AES) are in agreement at the 95% confidence level.