Design of a label-free aptasensor for electrochemical determination of hemoglobin: investigation of the peroxidase-like activity of hemoglobin for the sensing of different substrates.

The unbalanced hemoglobin level in biological fluids can cause several diseases; hence it can be used as a biomarker for diagnosis. We aim, in the present study, to construct a label-free electrochemical aptasensor for the quantification of hemoglobin. For that, a conjugate of L-cysteine and gold nanoparticles was used for the aptamer immobilization on screen printed carbon electrodes. Using square wave voltammetry, the calibration plot was obtained and it was linear in the range of 50 ng ml-1 to 36 000 ng ml-1 while the detection limit was 1.2 ng ml-1. After the binding of Hb on the modified screen-printed carbon electrode surface, the peroxidase-like activity of the bound hemoglobin was explored in the quantification of different substrates. Hydrogen peroxide and nitrite were chosen as model analytes. Amperometric measurements showed wide linear ranges: 0.2 µM-7.7 mM and 3.6 nM-1.3 mM for H2O2 and nitrite, respectively, with detection limits of 0.044 µM and 0.55 nM. In the proposed strategy, the aptamer provides excellent orientation and a biocompatible environment for hemoglobin whose catalytic activity plays a key role in H2O2 and nitrite analysis.

Development of a label-free electrochemical aptasensor based on diazonium electrodeposition: Application to cadmium detection in water.

In this study we have developed a new aptasensor for cadmium (Cd2+) detection in water. Gold electrode surface has been chemically modified by electrochemical reduction of diazonium salt (CMA) with carboxylic acid outward from the surface. This was used for amino-modified cadmium aptamer immobilization through carbodiimide reaction. Chemical surface modification was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). This latter was also used for Cd2+ detection. The aptasensor has exhibited a good linear relationship between the logarithm of the Cd2+ concentration and the impedance changes in the range from 10-3 to 10-9 M with a correlation R2 of 0.9954. A high sensitivity was obtained with a low limit of detection (LOD) of 2.75*10-10 M. Moreover, the developed aptasensor showed a high selectivity towards Cd2+ when compared to other interferences such as Hg2+, Pb2+ and Zn2+. The developed aptasensor presents a simple and sensitive approach for Cd2+detection in aqueous solutions with application for trace Cd2+ detection in spring water samples.

Fabrication of AuNPs/MWCNTS/Chitosan Nanocomposite for the Electrochemical Aptasensing of Cadmium in Water.

Cadmium (Cd2+) is one of the most toxic heavy metals causing serious health problems; thus, designing accurate analytical methods for monitoring such pollutants is highly urgent. Herein, we report a label-free electrochemical aptasensor for cadmium detection in water. For this, a nanocomposite combining the advantages of gold nanoparticles (AuNPs), carbon nanotubes (CNTs) and chitosan (Cs) was constructed and used as immobilization support for the cadmium aptamer. First, the surface of a glassy carbon electrode (GCE) was modified with CNTs-CS. Then, AuNPs were deposited on CNTs-CS/GCE using chrono-amperometry. Finally, the immobilization of the amino-modified Cd-aptamer was achieved via glutaraldehyde cross-linking. The different synthesis steps of the AuNPs/CNTs/CS nano assembly were characterized by cyclic voltammetry (CV). Electrochemical impedance spectroscopy (EIS) was employed for cadmium determination. The proposed biosensor exhibited excellent performances for cadmium detection at a low applied potential (-0.5 V) with a high sensitivity (1.2 KΩ·M-1), a detection limit of 0.02 pM and a wide linear range (10-13-10-4 M). Moreover, the aptasensor showed a good selectivity against the interfering ions: Pb2+; Hg2+ and Zn2+. Our electrochemical biosensor provides a simple and sensitive approach for Cd2+ detection in aqueous solutions, with promising applications in the monitoring of trace amounts of heavy metals in real samples.