Detection of H. pylori outer membrane protein (HopQ) biomarker using electrochemical impedimetric immunosensor with polypyrrole nanotubes and carbon nanotubes nanocomposite on screen-printed carbon electrode.

Helicobacter pylori (H. pylori) is classified as a class I carcinogen that colonizes the human gastrointestinal (GI) tract. The detection at low concentrations is crucial in combatting H. pylori. HopQ protein is located on H. pylori's outer membrane and is expressed at an early stage of contamination, which signifies it as an ideal biomarker. In this study, we presented the development of an electrochemical impedimetric immunosensor for the ultra-sensitive detection of HopQ at low concentrations. The sensor employed polypyrrole nanotubes (PPy-NTs) and carboxylated multi-walled carbon nanotubes (MWCNT-COOH) nanocomposite. PPy-NTs were chosen for their excellent conductivity, biocompatibility, and redox capabilities, simplifying sample preparation by eliminating the need to add redox probes upon measurement. MWCNT-COOH provided covalent binding sites for HopQ antibodies (HopQ-Ab) on the biosensor surface. Characterization of the biosensor was performed using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), contact angle measurements, and electrochemical impedance spectroscopy (EIS), complemented by numerical semiempirical quantum calculations. The results demonstrated a dynamic linear range of 5 pg/mL to 1.063 ng/mL and an excellent selectivity, with the possibility of excluding interference using EIS data, specifically charge transfer resistance and double-layer capacitance as multivariants for the calibration curve. Using two EIS components, the limit of detection is calculated to be 2.06 pg/mL. The biosensor was tested with a spiked drinking water sample and showed a signal recovery of 105.5% when detecting 300 pg/mL of HopQ. This novel H. pylori biosensor offers reliable, simple, portable, and rapid screening of the bacteria.

Interfacial Characterization of Polypyrrole/AuNP Composites towards Electrocatalysis of Ascorbic Acid Oxidation.

Polypyrrole (PPy) is an interesting conducting polymer due to its good environmental stability, high conductivity, and biocompatibility. The association between PPy and metallic nanoparticles has been widely studied since it enhances electrochemical properties. In this context, gold ions are reduced to gold nanoparticles (AuNPs) directly on the polymer surface as PPy can be oxidized to an overoxidized state. This work proposes the PPy electrochemical synthesis followed by the direct reduction of gold on its surface in a fast reaction. The modified electrodes were characterized by electronic microscopic and infrared spectroscopy. The effect of reduction time on the electrochemical properties was evaluated by the electrocatalytic properties of the obtained material from the oxidation of ascorbic acid (AA) and electrochemical impedance spectroscopy studies. The presence of AuNPs improved the AA electrocatalysis by reducing oxidation potential and lowering charge transfer resistance. EIS data were fitted using a transmission line model. The results indicated an increase in the electronic transport of the polymeric film in the presence of AuNPs. However, PPy overoxidation occurs when the AuNPs' deposition is higher than 30 s. In PPy/AuNPs 15 s, smaller and less agglomerated particles were formed with fewer PPy overoxidized, confirming the observed electrocatalytic behavior.

Effect of low and high methoxyl citrus pectin on the properties of polypyrrole based electroactive hydrogels.

Electroactive hydrogels were prepared using commercial citric pectin, either raw (PC) or purified through dialysis (dPC), and chemically synthesized polypyrrole (PPy). 1H NMR analyses showed that PC is a low methoxyl pectin (degree of methoxylation, DM=46%) and dPC is a high methoxyl pectin (DM=77%). The pyrrole polymerization was monitored through UV-vis spectroscopy and both samples were observed to be good stabilizers for PPy in aqueous medium. The dispersions were used to prepare the hydrogels h-PC-PPy and h-dPC-PPy. The hydrogel h-dPC-PPy has a higher swelling index (SI≈25%) at pH 1.2 than the hydrogel h-PC-PPy (SI≈7%). Contrastingly, at pH 6.8 both hydrogels lost their mechanical integrity. Raman spectroscopy revealed that PPy is more oxidized in h-PC-PPy. Nevertheless, both hydrogels are electroactive and therefore can be considered for applications in which the control of the degree of swelling is desired.

How the charge-neutrality level of interface states controls energy level alignment in cathode contacts of organic bulk-heterojunction solar cells.

Electronic equilibration at the metal-organic interface, leading to equalization of the Fermi levels, is a key process in organic optoelectronic devices. How the energy levels are set across the interface determines carrier extraction at the contact and also limits the achievable open-circuit voltage under illumination. Here, we report an extensive investigation of the cathode energy equilibration of organic bulk-heterojunction solar cells. We show that the potential to balance the mismatch between the cathode metal and the organic layer Fermi levels is divided into two contributions: spatially extended band bending in the organic bulk and voltage drop at the interface dipole layer caused by a net charge transfer. We scan the operation of the cathode under a varied set of conditions, using metals of different work functions in the range of ∼2 eV, different fullerene acceptors, and several cathode interlayers. The measurements allow us to locate the charge-neutrality level within the interface density of sates and calculate the corresponding dipole layer strength. The dipole layer withstands a large part of the total Fermi level mismatch when the polymer:fullerene blend ratio approaches ∼1:1, producing the practical alignment between the metal Fermi level and the charge-neutrality level. Origin of the interface states is linked with fullerene reduced molecules covering the metal contact. The dipole contribution, and consequently the band bending, is highly sensitive to the nature and amount of fullerene molecules forming the interface density of states. Our analysis provides a detailed picture of the evolution of the potentials in the bulk and the interface of the solar cell when forward voltage is applied or when photogeneration takes place.

Recombination in Organic Bulk Heterojunction Solar Cells: Small Dependence of Interfacial Charge Transfer Kinetics on Fullerene Affinity.

We investigate the causes for obtaining higher open-circuit voltage in solar cells that use a fullerene with a smaller electron affinity. Using impedance spectroscopy technique, we show that the change of fullerene LUMO energy has very little influence on the kinetic rate of charge transfer across the interface. In terms of the Marcus theory, large reorganization energy values govern the recombination kinetic rate, which is only slightly dependent on the fullerene LUMO energy, and also depends weakly on the energy location of recombining carriers within the broad density of states. Since the recombination rate is very similar in the different devices, we conclude that the larger open-circuit voltage is due to the larger donor HOMO/acceptor LUMO offset.