New electrochemically improved tetrahedral amorphous carbon films for biological applications

Carbon based materials have been frequently used to detect different biomolecules. For example high sp3 containing hydrogen free diamond-like carbon (DLC) possesses many properties that are beneficial for biosensor applications. Unfortunately, the sensitivities of the DLC electrodes are typically low. Here we demonstrate that by introducing topography on the DLC surface and by varying its layer thickness, it is possible to significantly increase the sensitivity of DLC thin film electrodes towards dopamine. The electrode structures are characterized in detail by atomic force microscopy (AFM) and conductive atomic force microscopy (C-AFM) as well as by transmission electron microscopy (TEM) combined with electron energy loss spectroscopy (EELS). With cyclic voltammetry (CV) measurements we demonstrate that the new improved DLC electrode has a very wide water window, but at the same time it also exhibits fast electron transfer rate at the electrode/solution interface. In addition, it is shown that the sensitivity towards dopamine is increased up to two orders of magnitude in comparison to the previously fabricated DLC films, which are used as benchmarks in this investigation. Finally, it is shown, based on the cyclic voltammetry measurements that dopamine exhibits highly complex behavior on top of these carbon electrodes.The authors T.L, V.P., S.S., T.P., and J.K., would like to acknowledge the National Agency for Technology and Innovation (grant number 211488) and Aalto University (grant number 902380) for the financial support

Electrochemical reactions of catechol, methylcatechol and dopamine at tetrahedral amorphous carbon (ta-C) thin film electrodes

The electrochemical reactions of dopamine, catechol and methylcatechol were investigated at tetrahedral amorphous carbon (ta-C) thin film electrodes. In order to better understand the reaction mechanisms of these molecules, cyclic voltammetry with varying scan rates was carried out at different pH values in H2SO4 and PBS solutions. The results were compared to the same redox reactions taking place at glassy carbon (GC) electrodes. All three catechols exhibited quasi-reversible behavior with sluggish electron transfer kinetics at the ta-C electrode. At neutral and alkaline pH, rapid coupled homogeneous reactions followed the oxidation of the catechols to the corresponding o-quinones and led to significant deterioration of the electrode response. At acidic pH, the extent of deterioration was considerably lower. All the redox reactions showed significantly faster electron transfer kinetics at the GC electrode and it was less susceptible toward surface passivation. An EC mechanism was observed for the oxidation of dopamine at both ta-C and GC electrodes and the formation of polydopamine was suspected to cause the passivation of the electrodes.Authors wish to acknowledge the financial support by the Finnish Parkinson Foundation (T.P.), the Finnish Funding Agency for Innovation (grant number 211488) (T.P., S.S. and T.L.), the Academy of Finland (grant number 285015) (T.L.) and MINECO project CTQ2013-44083-P (J.F.M.)

Spatial distribution of the electrical potential and ion concentration in the downstream area of atmospheric pressure remote plasma

This paper presents the results from an experimental study of the ion flux characteristics behind the remote plasma zone in a vertical tube reaction chamber for atmospheric pressure plasma enhanced chemical vapor deposition. Capacitively coupled radio frequency plasma was generated in pure He and gas mixtures: He–Ar, He–O2, He–TEOS. We previously used the reaction system He–TEOS for the synthesis of self-assembled structures of silicon dioxide nanoparticles. It is likely that the electrical parameters of the area, where nanoparticles have been transported from the synthesis zone to the substrate, play a significant role in the self-organization processes both in the vapor phase and on the substrate surface. The results from the spatial distribution of the electrical potential and ion concentration in the discharge downstream area measured by means of the external probe of original design and the special data processing method are demonstrated in this work. Positive and negatives ions with maximum concentrations of 106–107 cm−3 have been found at 10–80 mm distance behind the plasma zone. On the basis of the revealed distributions for different gas mixtures, the physical model of the observed phenomena is proposed. The model illustrates the capability of the virtual ion emitter formation behind the discharge gap and the presence of an extremum of the electrical potential at the distance of approximately 10−2–10−1 mm from the grounded electrode.Peer reviewe

Glutamate detection by amino functionalized tetrahedral amorphous carbon surfaces

Peer reviewe

Electrochemical detection of hydrogen peroxide on platinum-containing tetrahedral amorphous carbon sensors and evaluation of their biofouling properties

Hydrogen peroxide is the product of various enzymatic reactions, and is thus typically utilized as the analyte in biosensors. However, its detection with conventional materials, such as noble metals or glassy carbon, is often hindered by slow kinetics and biofouling of the electrode. In this study electrochemical properties and suitability to peroxide detection as well as ability to resist biofouling of Pt-doped ta-C samples were evaluated. Pure ta-C and pure Pt were used as references. According to the results presented here it is proposed that combining ta-C with Pt results in good electrocatalytic activity towards H2O2 oxidation with better tolerance towards aqueous environment mimicking physiological conditions compared to pure Pt. In biofouling experiments, however, both the hybrid material and Pt were almost completely, blocked after immersion in protein-containing solutions and did not produce any peaks for ferrocenemethanol oxidation or reduction. On the contrary, it was still possible to obtain clearpeaks for H2O2 oxidation with them after similar treatment Moreover, quartz crystal microbalance experiment showed less protein adsorption on the hybrid sample compared to Pt which is also supported by the electrochemical biofouling experiments for H2O2 detection. (C) 2015 Elsevier B.V. All rights reserved.Peer reviewe

Structural insights into TRPV2 activation by small molecules

Transient receptor potential vanilloid 2 (TRPV2) is involved in many critical physiological and pathophysiological processes, making it a promising drug target. Here we present cryo-electron microscopy (cryo-EM) structures of rat TRPV2 in lipid nanodiscs activated by 2-aminoethoxydiphenyl borate (2-APB) and propose a TRPV2-specific 2-ABP binding site at the interface of S5 of one monomer and the S4-S5 linker of the adjacent monomer. In silico docking and electrophysiological studies confirm the key role of His521 and Arg539 in 2-APB activation of TRPV2. Additionally, electrophysiological experiments show that the combination of 2-APB and cannabidiol has a synergetic effect on TRPV2 activation, and cryo-EM structures demonstrate that both drugs were able to bind simultaneously. Together, our cryo-EM structures represent multiple functional states of the channel, providing a native picture of TRPV2 activation by small molecules and a structural framework for the development of TRPV2-specific activators

Carbon Nanostructure Based Platform for Enzymatic Glutamate Biosensors

Hydrogen peroxide (H₂O₂) is an important molecule produced in various enzymatic reactions. It is especially important in electrochemical, enzymatic biosensors detecting electroinactive analytes, such as glucose, cholesterol, and glutamate. Thus, there is a strong need for materials that have high affinity for H₂O₂ oxidation or reduction as well as enable immobilization and sustain enzyme activity without any additional polymer layers. Carbon nanofibers (CNFs) directly grown on tetrahedral amorphous carbon (ta-C) are feasible candidates for this purpose as they possess a reasonably wide water window (1.8 V) and good activity for H₂O₂ reduction in physiological pH and contain innately large amounts of suitable functional groups for enzyme immobilization. Here we show their use in ultrafast (<0.05 s) detection of H₂O₂ with the limit of detection of 26 μM and sensitivity of 0.221 A M^–1 cm^–2. Moreover, we show that ta-C/CNF hybrids can be used directly without the mass-transfer limiting polymer layers as effective immobilization platforms for glutamate oxidase for further applications in ultrafast (<0.05 s) glutamate detection. Finally, rat glial cells cultured on CNFs grown from ta-C without any additional coatings, such as polylysine, showed good adhesion on CNFs and no signs of cytotoxicity, indicating suitability of the material for future in vivo applications. This simplified and miniaturized structure provides an extremely interesting platform for various different enzyme-based electrochemical sensors

Structural insights into TRPV2 activation by small molecules.

Transient receptor potential vanilloid 2 (TRPV2) is involved in many critical physiological and pathophysiological processes, making it a promising drug target. Here we present cryo-electron microscopy (cryo-EM) structures of rat TRPV2 in lipid nanodiscs activated by 2-aminoethoxydiphenyl borate (2-APB) and propose a TRPV2-specific 2-ABP binding site at the interface of S5 of one monomer and the S4-S5 linker of the adjacent monomer. In silico docking and electrophysiological studies confirm the key role of His521 and Arg539 in 2-APB activation of TRPV2. Additionally, electrophysiological experiments show that the combination of 2-APB and cannabidiol has a synergetic effect on TRPV2 activation, and cryo-EM structures demonstrate that both drugs were able to bind simultaneously. Together, our cryo-EM structures represent multiple functional states of the channel, providing a native picture of TRPV2 activation by small molecules and a structural framework for the development of TRPV2-specific activators