Abstract: | The present work demonstrates the use of mesoporous nanofibers for the enhanced analytical performance of electrochemical biosensor. By exploiting the phase separation property of the block copolymers, a simple three‐step process was used to generate the porosity in the nanofibers. Here we present the effect of the porosity on the sensing ability of the electrospun PS‐b‐PMMA nanofibers. The functional groups present on the nanofiber surface were characterized using DPV. The nanofibers modified electrode showed a large decrease in the oxidation current with the increase in the pH from 4.2 to 6.8 for the anionic redox couple whereas the change in the current is negligible for a neutral redox couple, this suggested the presence of ‐COOH groups. A one‐step process was used for the immobilization of biotin. There were about 35.5 % and 66.6 % decrease in the redox current for the as‐spun and porous nanofibers after functionalization respectively which indicate the presence of a high amount of active sites in the porous nanofibers. Finally, the sensor response was studied using streptavidin (1μg/ml–1fg/ml) as a model analyte. CV studies showed a 2.7‐fold increase whereas DPV showed a 6‐fold increase in the sensitivity for the porous nanofibers as compared to the as‐spun nanofibers. |