Heat treating nitrogen-doped multiwalled carbon nanotubes containing up to six different types of nitrogen functionalities transforms particular nitrogen functionalities into other types which are more catalytically active toward oxygen reduction reactions (ORR). In the first stage, the unstable pyrrolic functionalities transform into pyridinic functionalities followed by an immediate transition into quaternary center and valley nitrogen functionalities. By measuring the electrocatalytic oxidation reduction current for the different samples, we achieve information on the catalytic activity connected to each type of nitrogen functionality. Through this, we conclude that quaternary nitrogen valley sites, N-Q(valley), are the most active sites for ORR in N-CNTs. The number of electrons transferred in the ORR is determined from ring disk electrode and rotating ring disk electrode measurements. Our measurements indicate that the ORR processes proceed by a direct four-electron pathway for the N-Q(valley) and the pyridinic sites while it proceeds by an indirect two-electron pathway via hydrogen peroxide at the N-Q(center) sites. Our study gives both insights on the mechanism of ORR on different nitrogen functionalities in nitrogen-doped carbon nanostructures and it proposes how to treat samples to maximize the catalytic efficiency of such samples.

Pro-inflammatory S100A9 protein is increasingly recognized as an important contributor to inflammation-related neurodegeneration. Here, we provide insights into S100A9 specific mechanisms of action in Alzheimer’s disease (AD). Due to its inherent amyloidogenicity S100A9 contributes to amyloid plaque formation together with Aβ. In traumatic brain injury (TBI) S100A9 itself rapidly forms amyloid plaques, which were reactive with oligomer-specific antibodies, but not with Aβ and amyloid fibrillar antibodies. They may serve as precursor-plaques for AD, implicating TBI as an AD risk factor. S100A9 was observed in some hippocampal and cortical neurons in TBI, AD and non-demented aging. In vitro S100A9 forms neurotoxic linear and annular amyloids resembling Aβ protofilaments. S100A9 amyloid cytotoxicity and native S100A9 pro-inflammatory signaling can be mitigated by its co-aggregation with Aβ, which results in a variety of micron-scale amyloid complexes. NMR and molecular docking demonstrated transient interactions between native S100A9 and Aβ. Thus, abundantly present in AD brain pro-inflammatory S100A9, possessing also intrinsic amyloidogenic properties and ability to modulate Aβ aggregation, can serve as a link between the AD amyloid and neuroinflammatory cascades and as a prospective therapeutic target.Electronic supplementary materialThe online version of this article (doi:10.1007/s00401-013-1208-4) contains supplementary material, which is available to authorized users.

Graphene nanoscrolls are Archimedean-type spirals formed by rolling single-layer graphene sheets. Their unique structure makes them conceptually interesting and understanding their formation gives important information on the manipulation and characteristics of various carbon nanostructures. Here we report a 100% efficient process to transform nitrogen-doped reduced graphene oxide sheets into homogeneous nanoscrolls by decoration with magnetic g-Fe 2 O 3 nanoparticles. Through a large number of control experiments, magnetic characterization of the decorated nanoparticles, and ab initio calculations, we conclude that the rolling is initiated by the strong adsorption of maghemite nanoparticles at nitrogen defects in the graphene lattice and their mutual magnetic interaction. The nanoscroll formation is fully reversible and upon removal of the maghemite nanoparticles, the nanoscrolls return to open sheets. Besides supplying information on the rolling mechanism of graphene nanoscrolls, our results also provide important information on the stabilization of iron oxide nanoparticles.

We report here on the electroreduction of p-benzoquinone (BQ) or H2O2 as a new trigger for simple, fast, uniform, and controllable electrodeposition of chitosan (CS) hydrogels and biosensing nanocomposite films of CS, multiwalled carbon nanotubes (MWCNTs), and glucose oxidase (GOD). The multiparameter electrochemical quartz crystal microbalance (EQCM) based on crystal electroacoustic impedance analysis was used to dynamically monitor the deposition processes. When the EQCM Au electrode was immersed in a weakly acidic solution (here pH 5.1 acetic buffer) containing BQ (or H2O2) and CS, the proton consumption during BQ (or H2O2) electroreduction increased the local solution pH near the electrode surface and led to the deposition of CS hydrogel on the electrode surface at local pH near and above the pKa value of CS. The concentration of BQ (or H2O2) required for CS electrodeposition was theoretically evaluated based on an electrogenerated base-to-acid titration model and supported by experiments. Co-deposition of GOD and MWCNTs with the CS hydrogel was achieved, and the resulting MWCNTs-CS-GOD nanocomposite films were demonstrated for glucose biosensing. The MWCNTs-CS-GOD enzyme electrode prepared by BQ reduction exhibited a current sensitivity of 6.7 microA mM-1 cm-2 to glucose, and the linear range for glucose detection at 0.7 V vs SCE was from 5 microM to 8 mM, with a detection limit of 2 microM and a Michaelis-Menten constant of 6.8 mM. The BQ-electroreduction protocol exhibited the best sensor performance, as compared with H2O2-reduction and previously reported water-reduction values. The present protocol via electroreduction of a deliberately added oxidant that is accompanied by a local pH change is highly recommended for wider applications in pH-dependent deposition of other films.

The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium:tungsten ¼ 1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are B1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.

Graphene and its derivatives hold great potential as support for nanocatalyst in various energy applications, such as fuel cells, batteries, and capacitors. In this work, we used density functional theory to analyze substrate effect on the electrocatalytic activity of Pt–Ni bimetallic nanoparticles for oxygen reduction reaction (ORR). The dissociative mechanism is used to evaluate the ORR performance (energy barrier for O2 dissociation, free energy of intermediates, d-band center, overpotential, and electrochemical activity) for a Pt–Ni core–shell-like nanoparticle (PtNiCS) deposited on nondefective graphene (GS) or nitrogen-doped graphene (N-GS). The electronic and catalytic properties of PtNiCS on N-GS designate N-doped graphene as the best substrate to use for ORR, showing better interaction with the bimetallic cluster, improved charge transfer between constitutes, and a superior ORR performance when compared to PtNiCS on GS. The N-GS has a significant effect in reducing the energy barrier for O2 dissociation and decrease the energetic stability of HO* intermediates, resulting in enhanced ORR activity compared with the PtNiCS on GS. In addition, the strong interaction between PtNiCS cluster and N-GS substrate may lead to an improved long-term stability of the catalytic particle during ORR cycles.

We report on a novel sensing platform for H2O2 and glucose based on immobilization of palladium-helical carbon nanofiber (Pd-HCNF) hybrid nanostructures and glucose oxidase (GOx) with Nafion on a glassy carbon electrode (GCE). HCNFs were synthesized by a chemical vapor deposition process on a C60-supported Pd catalyst. Pd-HCNF nanocomposites were prepared by a one-step reduction free method in dimethylformamide (DMF). The prepared materials were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. The Nafion/Pd-HCNF/GCE sensor exhibits excellent electrocatalytic sensitivity toward H2O2 (315 mA M(-1) cm(-2)) as probed by cyclic voltammetry (CV) and chronoamperometry. We show that Pd-HCNF-modified electrodes significantly reduce the overpotential and enhance the electron transfer rate. A linear range from 5.0 μM to 2.1 mM with a detection limit of 3.0 μM (based on the S/N = 3) and good reproducibility were obtained. Furthermore, a sensing platform for glucose was prepared by immobilizing the Pd-HCNFs and glucose oxidase (GOx) with Nafion on a glassy carbon electrode. The resulting biosensor exhibits a good response to glucose with a wide linear range (0.06-6.0 mM) with a detection limit of 0.03 mM and a sensitivity of 13 mA M(-1) cm(-2). We show that small size and homogeneous distribution of the Pd nanoparticles in combination with good conductivity and large surface area of the HCNFs lead to a H2O2 and glucose sensing platform that performs in the top range of the herein reported sensor platforms.

Pro-inflammatory protein S100A9 was established as a biomarker of dementia progression and compared with others such as Aβ(1-42) and tau-proteins. CSF samples from 104 stringently diagnosed individuals divided into five subgroups were analyzed, including nondemented controls, stable mild cognitive impairment (SMCI), mild cognitive impairment due to Alzheimer's disease (MCI-AD), Alzheimer's disease (AD), and vascular dementia (VaD) patients. ELISA, dot-blotting, and electrochemical impedance spectroscopy were used as research methods. The S100A9 and Aβ(1-42) levels correlated with each other: their CSF content decreased already at the SMCI stage and declined further under MCI-AD, AD, and VaD conditions. Immunohistochemical analysis also revealed involvement of both Aβ(1-42) and S100A9 in the amyloid-neuroinflammatory cascade already during SMCI. Tau proteins were not yet altered in SMCI; however their contents increased during MCI-AD and AD, diagnosing later dementia stages. Thus, four biomarkers together, reflecting different underlying pathological causes, can accurately differentiate dementia progression and also distinguish AD from VaD.