Electrografting a Hybrid Bilayer Membrane via Diazonium Chemistry for Electrochemical Impedance Spectroscopy of Amyloid-ß Aggregation.

Herein, a novel hybrid bilayer membrane is introduced as a platform to study the aggregation of amyloid-ß1-42 (Aß1-42) peptide on surfaces. The first layer was covalently attached to a glassy carbon electrode (GCE) via diazonium electrodeposition, which provided a highly stable template for the hybrid bilayer formation. To prepare the long-chain hybrid bilayer membrane (lcHBLM)-modified electrodes, GCE surfaces were modified with 4-dodecylbenzenediazonium (DDAN) followed by the modification with dihexadecyl phosphate (DHP) as the second layer. For the preparation of short-chain hybrid bilayer membrane (scHBLM)-modified electrodes, GCE surfaces were modified with 4-ethyldiazonium (EDAN) as the first layer and bis(2-ethylhexyl) phosphate (BEHP) was utilized as the second layer. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to characterize the bilayer formation. Both positively charged [Ru(NH3)6]3+ and negatively charged ([Fe(CN)6]3-/4-) redox probes were used for electrochemical characterization of the modified surfaces using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). EIS results showed a decrease in charge transfer resistance (Rct) upon incubation of Aß1-42 on the hybrid bilayer-modified surfaces. This framework provides a promising electrochemical platform for designing hybrid bilayers with various physicochemical properties to study the interaction of membrane-bound receptors and biomolecules on surfaces.

Revisiting the nitrite reductase activity of hemoglobin with differential pulse voltammetry.

Nitric oxide (NO) is an omnipresent signalling molecule in all vertebrates. NO modulates blood flow and neural activity. Nitrite anion is one of the most important sources of NO. Nitrite is reduced to NO by various physiological mechanisms including reduction by hemoglobin in vascular system. In this study, nitrite reductase activity (NRA) of hemoglobin is reported using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in a wide potential window from +0.3 V to -1.3 V (vs. Ag/AgCl). To the best of our knowledge, a detailed look into NRA of hemoglobin is proposed here for the first time. Our results indicated two different regimes for reduction of nitrite by hemoglobin in its Fe(II) and Fe(I) states. Both reactions showed a reversible behaviour in the time scale of the experiments. The first reduction displayed a normal redox behaviour, while the latter one had the characteristics of a catalytic electro-reduction/oxidation. The reduction in Fe(II) state was selected as a tool for comparing the NRA of hemoglobin (Hb) and hemoglobin-S (Hb-S) under native-like conditions in a didodecyldimethyl ammonium bromide (DDAB) liquid crystal film. These investigations lay the prospects and guidelines for understanding the direct electrochemistry of hemoglobin utilizing a simplified mediator-free platform.

Electrochemical Detection of Gallic Acid-Capped Gold Nanoparticles Using a Multiwalled Carbon Nanotube-Reduced Graphene Oxide Nanocomposite Electrode.

Recently, a plethora of ecofriendly methods have been developed for the synthesis of AuNPs using a multitude of biogenic agents. Polyphenols from plants are particularly attractive for producing AuNPs because in addition to helping with the synthesis of AuNPs, the polyphenol capping of the NPs can be used as a platform for versatile applications. Polyphenol-capped AuNPs could also make the detection of AuNPs possible, should they be released into the environment. Because polyphenols are redox-active, they can be used as a probe to detect AuNPs using electrochemical techniques. In this work, we have developed an MWCNT-rGO nanocomposite electrode for the sensitive detection of AuNPs capped with gallic acid (GA, a green-tea-derived polyphenol) using differential pulse voltammetry (DPV). The reduction of gallic acid-capped AuNPs was used as the quantification signal, and the calibration curve displayed a detection limit of 2.57 pM. Using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), we have shown that the modification of the electrode surface with an MWCNT-rGO hybrid nanocomposite resulted in a 10-fold increase in current response leading to the sensitive detection of GA-AuNPs compared to unmodified electrodes. We have also demonstrated the applicability of the electrochemical sensor in detecting GA-AuNPs in various analytical matrixes such as human serum and natural creek water (Highland Creek, ON) with good recovery.