A sensor for the enzymatic activity and inhibition of the 20S proteasome was developed by immobilizing the synthetic peptide ABZ-VVSYAMG-(O2Oc)2-OH at Au electrodes. The detection principle is based on the elec-troactivity of ABZ, part of the ABZ-VVSY-OH moiety released from the peptide upon 20S proteasome chymo-trypsin action. The peptide was immobilized on a para-amino thiophenol (PATP) self-assembled monolayer on Au electrode by cross-linking its amino group to the -(O2Oc)2-OH moiety of the peptide (Au/PATP/peptide). The immobilization of the peptide and its interaction with 20S proteasome was investigated by SEM, QCM, SPR, ATR-FTIR and electrochemistry. The activity of 20S proteasome was assessed electrochemically by cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) after the immersion Au/PATP/peptide in 20S proteasome solution. CV study showed a decrease in both capacitive and faradaic currents corresponding to the ABZ-VVSY-OH removal, allowing the quantification of the 20S proteasome activity. The EIS study revealed that the resis-tance corresponding to charge transfer reactions at the peptide/solution interface correlated to the ABZ redox reaction, decreased linearly with increasing the incubation time in 20S proteasome solution. The perfected assay was applied for the investigation of the inhibitory effect of one synthetic, bortezomib, and two naturally occurring, epoxomicin, and lactacystin inhibitors.

The concentration of thyroxine hormone is linked to a large variety of medical conditions, where the best therapy is hormone substitution, through administration of levothyroxine (LT4) medication. Herewith, the detection of these biomolecules still lacks a simple, reliable tool, such as label-free sensors.In this work, the performances of commercial screen-printed carbon electrodes, containing different nanostructured materials (carbon nanotubes, graphene, and gold nanoparticles), used as sensors for LT4 detection, were described and compared. Electrochemical methods were used for the characterization of the nanostructure-based sensors. Several optimization steps were undertaken to achieve optimum performances for selective LT4 quantification. The redox behaviour of LT4 at sensors surface together with the interfacial changes, which occur due to the interaction between nanostructures and LT4, were studied by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Differential pulse voltammetry (DPV) was used for LT4 detection, where best performances were obtained in the presence of carbon nanotubes, with a detection limit of 30 nM.

Curcumin (CR) is a natural antioxidant compound extracted from Curcuma longa (turmeric). Until now, researches related to the incorporation of CR into layered double hydroxides (LDHs) were focused only on hybrid structures based on a MgxAl-LDH matrix. Our studies were extended towards the incorporation of CR in another type of LDH-matrix (Zn3Al-LDH) which could have an even more prolific effect on the antioxidant activity due to the presence of Zn. Four CR-modified Zn3Al-LDH solids were synthesized, e.g., PZn3Al-CR(Aq), PZn3Al-CR(Et), RZn3Al-CR(Aq) and RZn3Al-CR(Et) (molar ratio CR/Al = 1/10, where P and R stand for the preparation method (P = precipitation, R = reconstruction), while (Aq) and (Et) indicate the type of CR solution, aqueous or ethanolic, respectively). The samples were characterized by XRD, Attenuated Total Reflectance Fourier Transformed IR (ATR-FTIR) and diffuse reflectance (DR)-UV-Vis techniques and the CR-release was investigated in buffer solutions at different pH values (1, 2, 5, 7 and 8). XRD results indicated a layered structure for PZn3Al-CR(Aq), PZn3Al-CR(Et), RZn3Al-CR(Aq) impurified with ZnO, while RZn3Al-CR(Et) contained ZnO nano-particles as the main crystalline phase. For all samples, CR-release revealed a decreasing tendency towards the pH increase, and higher values were obtained for RZn3Al-CR(Et) and PZn3Al-CR(Et) (e.g., 45% and 25%, respectively at pH 1).

This work reports the use of electrospun conductive gold covered polycaprolactone fibers for the quantification of dissolved O-2. The morphologies of the electrospun fibers obtained at a static and a dynamic drum collector were investigated by scanning electron microscopy. The reduction process of O-2 at negative potentials is analyzed by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) in sodium phosphate buffer (NaPB) pH 7.0 and in cellular media pH 7.4. The electrochemical sensing performance of Au/PCL towards O-2 quantification in NaPB and cellular media is compared by using three electrochemical techniques: cyclic and linear sweep voltammetry and EIS. Measurements are done in a two electrode configuration, using a silver wire as reference, to show the applicability of the method for O-2 quantification in cellular culture media.

We investigate band bending effects occurring at the interface between atomically clean Ge(001) and molecular beam epitaxy (MBE) deposited copper and platinum. Low energy electron diffraction(LEED) confirmed the crystallinity of the surface, evidenced the formation of (2 x 1) and (1 x 2) reconstructions, and revealed that it is strongly affected with metal deposition. X-ray photoelectron spectroscopy (XPS) data let us assume a Stranski-Krastanov growth mechanism and confirmed that the observed band bending is associated to an ohmic contact in both cases. For the platinum contact, the high values of the apparent inelastic mean free path (IMFP) derived from the evolution of the XPS intensities indicate a prevalence of mixture of Pt with Ge nearby the interface. Pt deposited on Ge(001) does not behave like a Schottky contact, as one may have expected due to the higher work function of platinum. The observed effect is similar to the ease where interfacial Pt had a lower work function by 2.25/1.96 eV than that of metallic Pt. We propose a model to explain this fact by the effective mass variation or to the conduction band broadening due to the strong intermixing of platinum with germanium under the surface. (C) 2016 Elsevier B.V. All rights reserved.