Redox Mediation at 11-Mercaptoundecanoic Acid Self-Assembled Monolayers on Gold

Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and digital simulation techniques were used to investigate quantitatively the mechanism of electron transfer (ET) through densely packed and well-ordered self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid on gold, either pristine or modified by physically adsorbed glucose oxidase (GOx). In the presence of ferrocenylmethanol (FcMeOH) as a redox mediator, ET kinetics involving either solution-phase hydrophilic redox probes such as [Fe(CN)6]3-/4- or surface-immobilized GOx is greatly accelerated: [Fe(CN)6]3-/4- undergoes diffusion-controlled ET, while the enzymatic electrochemical conversion of glucose to gluconolactone is efficiently sustained by FcMeOH. Analysis of the results, also including the digital simulation of CV and EIS data, showed the prevalence of an ET mechanism according to the so-called membrane model that comprises the permeation of the redox mediator within the SAM and the intermolecular ET to the redox probe located outside the monolayer. The analysis of the catalytic current generated at the GOx/SAM electrode in the presence of glucose and FcMeOH allowed the high surface protein coverage suggested by X-ray photoelectron spectroscopy (XPS) measurements to be confirmed.

Nano-Electrochemical Characterization of a 3D Bioprinted Cervical Tumor Model

Current cancer research is limited by the availability of reliable in vivo and in vitro models that are able to reproduce the fundamental hallmarks of cancer. Animal experimentation is of paramount importance in the progress of research, but it is becoming more evident that it has several limitations due to the numerous differences between animal tissues and real, in vivo human tissues. 3D bioprinting techniques have become an attractive tool for many basic and applied research fields. Concerning cancer, this technology has enabled the development of three-dimensional in vitro tumor models that recreate the characteristics of real tissues and look extremely promising for studying cancer cell biology. As 3D bioprinting is a relatively recently developed technique, there is still a lack of characterization of the chemical cellular microenvironment of 3D bioprinted constructs. In this work, we fabricated a cervical tumor model obtained by 3D bioprinting of HeLa cells in an alginate-based matrix. Characterization of the spheroid population obtained as a function of culturing time was performed by phase-contrast and confocal fluorescence microscopies. Scanning electrochemical microscopy and platinum nanoelectrodes were employed to characterize oxygen concentrations - a fundamental characteristic of the cellular microenvironment - with a high spatial resolution within the 3D bioprinted cervical tumor model; we also demonstrated that the diffusion of a molecular model of drugs in the 3D bioprinted construct, in which the spheroids were embedded, could be measured quantitatively over time using scanning electrochemical microscop

Copper chloro-complexes concentrated solutions: An electrochemical study

Basic studies on concentrated solutions are becoming more and more important due to the practical industrial and geological applications. The use in redox flow batteries is one of the most important applications of these solutions. Specifically, in this paper we investigated high-concentrated copper chloro-complexes solutions with different additives. The concentration of ligands and additives affects the physicochemical and electrochemical properties of 2 M solutions of Cu(I) and Cu(II). Solutions with calcium chloride and HCl as Cl- source were investigated with Cu:Cl ratios of 1:5 and 1:7, the 1:5 Cu:Cl ratio being the best performing. The substitution of calcium chloride with ammonium chloride increased the conductivity. However, while the effect on the positive electrode process was not very evident, the reversibility of the copper deposition-stripping process was greatly improved. Orthophosphoric acid could be a viable additive to decrease the complexation of calcium with chloride anions and to improve the stability of Cu(II) chloro-complexes. Absorption spectroscopy demonstrated that phosphate ions do not coordinate copper(II) but lead to a shift in the distribution of copper chloro-complexes toward more coordinated species. Electrochemically, the increased availability of chloride anions in solution stabilized the Cu(II)-rich solution and led to increased reversibility of the Cu(II)/Cu(I) redox process

Enhanced Uptake and Phototoxicity of C60@albumin Hybrids by Folate Bioconjugation

Fullerenes are considered excellent photosensitizers, being highly suitable for photodynamic therapy (PDT). A lack of water solubility and low biocompatibility are, in many instances, still hampering the full exploitation of their potential in nanomedicine. Here, we used human serum albumin (HSA) to disperse fullerenes by binding up to five fullerene cages inside the hydrophobic cavities. Albumin was bioconjugated with folic acid to specifically address the folate receptors that are usually overexpressed in several solid tumors. Concurrently, tetramethylrhodamine isothiocyanate, TRITC, a tag for imaging, was conjugated to C-60@HSA in order to build an effective phototheranostic platform. The in vitro experiments demonstrated that: (i) HSA disperses C-60 molecules in a physiological environment, (ii) HSA, upon C-60 binding, maintains its biological identity and biocompatibility, (iii) the C-60@HSA complex shows a significant visible-light-induced production of reactive oxygen species, and (iv) folate bioconjugation improves both the internalization and the PDT-induced phototoxicity of the C-60@HSA complex in HeLa cells

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of stateof- the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50mVoverpotential). The Tafel slope of B130mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure

Redox active Double Wall Carbon Nanotubes show intrinsic anti-proliferative effects and modulate autophagy in cancer cells

In Double-Walled-Carbon-Nanotubes (DWCNTs) the outer shell screens the inner one from the external environment. As a consequence, the electronic properties of the smaller tube are enhanced and DWCNTs have therefore been advocated for a number of uses. In their raw form theymay contain small metallic clusters, left over from the catalytic process, that can give them a redox activity characterized by redox potentials in the range of one hundred millivolts and able to affect biological systems. Indeed, we find that redox active raw-DWCNTs inhibit rat colorectal cancer cell proliferation by blocking cells in the G2 phase through ROS generation by tumor cells. We show that raw-DWCNTs could also modulate autophagy in tumor cells through induction of intracellular acidification. To the best of our knowledge, this is the first time that DWCNTs have been found to inhibit proliferation and modulate autophagy in cancer cells. Our work further supports previous studies that provided promising results on the possibility of future applications of Carbon Nanotubes (CNTs) in nanomedicine