Cationic Rectifier Based on a Graphene Oxide-Covered Microhole: Theory and Experiment.

Cation transport through nanochannels in graphene oxide can be rectified to give ionic diode devices for future applications, for example, in desalination. A film of graphene oxide is applied to a 6 µm thick poly(ethylene terephthalate) substrate with a 20 µm diameter microhole and immersed in aqueous HCl solution. Strong diode effects are observed even at high ionic strength (0.5 M). Switching between open and closed states, microhole size effects, and time-dependent phenomena are explained on the basis of a simplified theoretical model focusing on the field-driven transport within the microhole region. In aqueous NaCl, competition between Na+ transport and field-driven heterolytic water splitting is observed but shown to be significant only at low ionic strength. Therefore, nanostructured graphene oxide is demonstrated to exhibit close to ideal behavior for future application in ionic diode desalination of seawater.

Effects of the dipolar double layer on elemental electrode processes at micro- and macro-interfaces.

Determination of heterogeneous rate constants of redox reactions or charge transfer resistances always involves ambiguities due to their participation in double layer (DL) capacitances and solution resistances. The rate constants determined by steady-state voltammograms at ultra-microelectrodes are inconsistent with time-dependent voltammograms, implying participation of the DL impedance. We examine controlling factors of DLs through the frequency-dependence of the capacitance on the basis of the definition of the current and the capacitance. The capacitance obeys the power law of the frequency. It is controlled by the orientation of a limited amount of solvent dipoles, independent of salts. Redox species, dipoles of which are oriented oppositely to the solvent dipoles, decrease the DL capacitance and make the value negative at high concentrations of the species. The decrease in the capacitance increases the real impedance, as predicted from the phase angle, yielding an extra resistance. This may be a ghost charge transfer resistance. However, there are actually a number of well-defined charge transfer resistances, which are observed as transferring rates through films on electrodes.

Preparation of Pt nanoclusters with different emission wavelengths and their application in Co2+ detection.

Differently colored fluorescent Pt nanoclusters (NCs) are easily prepared using polyethyleneimine as the stabilizing ligand and environmentally friendly L-ascorbic acid as the reducing agent. The quantum yields of the blue- (1:5), green- (1:20), and yellow-emitting (1:25) NCs are 4 %, 11 %, and 7 %, respectively. The fluorescent Pt NCs show excellent photostability and are sensitive to Co(2+) ions (with a detection limit of 500 nM).

Nobiletin induces inhibitions of Ras activity and mitogen-activated protein kinase kinase/extracellular signal-regulated kinase signaling to suppress cell proliferation in C6 rat glioma cells.

Ras, a small G-protein, physiologically directs cell proliferation and cell cycle via regulation of mitogen-activated protein kinase kinase (MEK)/extracellular signal-regulated kinase (ERK) signaling cascade. Dysregulation of Ras/MEK/ERK signaling has been reported to cause tumorigenesis and gliomas. Nobiletin, a citrus flavonoid, has been shown to have anti-tumor cells action. However, it remains elusive whether nobiletin could affect Ras activity. In this study, we provide the first evidence that nobiletin suppresses the proliferation by inhibiting Ras activity in C6 glioma cells, a rat glioma cell line. First, Ras pull-down assay showed that nobiletin inhibits Ras activity in a concentration-dependent manner in C6 cells. Second, farnesyltransferase inhibitor I, a Ras inhibitor, and U0126, a MEK inhibitor, induced an inhibition of the cell proliferation in C6 cells, while the cell proliferation was inhibited by nobiletin as well. Third, western blotting revealed that nobiletin showed inhibitory effects on MEK and ERK phopsphorylation levels in a concentration-dependent manner. Finally, such an inhibitory effect on the level of ERK phosphorylation by nobiletin was appreciably prevented by Gö6976, a selective inhibitor of conventional protein kinase Cs (PKCs) showing Ca(2+)-sensitivity, while GF109203X, a general inhibitor for PKCs, and BAPTA, a cell-permeable Ca(2+) chelator, to a lesser extent, suppressed a reduction of the phosphorylation. These findings suggest that the proliferation of C6 cells is Ras- and MEK/ERK signaling-dependent, and that nobiletin suppresses the cell proliferation by inhibiting Ras activity and MEK/ERK signaling cascade probably via a Ca(2+)-sensitive PKC-dependent mechanism. Thus, the natural compound has potential to be a therapeutic agent for glioma.

Inactivation mechanism of SARS-CoV-2 by ozone in aqueous and gas phases.

The comparison of the inactivation rate of SARS-CoV-2 by ozone in water with that in gas, based on data from references and experiments, has indicated the inactivation rate of the former is remarkably higher than that of the latter. To investigate the reason for this difference, we analyzed the reaction rate using a diffusional reaction model, in which ozone is carried by micro spherical viruses to inactivate the target viruses. Using this model, we can evaluate the amount of ozone required to inactivate a virus based on the ct value. We found that inactivation in gas phase requires 1014-1015 ozone molecules per virus virion, while the inactivation in aqueous phase requires 5×1010 to 5×1011 ozone molecules. This implies that the efficiency in gas phase is 200-20,000 times lower than that in aqueous phase. This is not attributed to the lower probability of collision in gas phase than in aqueous phase. Rather, it may be due to the fact that the ozone and radicals generated by ozone react and subsequently dissipate. We proposed the diffusion of ozone into a spherical virus at a steady state and the decomposition reaction model through radicals.

Participation in Negative Capacitance of Diffusion-Controlled Voltammograms of Hemin.

Hemin in dimethyl sulfoxide solution has exhibited voltammograms controlled by diffusion at glassy carbon electrodes for slow scan rates, although it is adsorbed slightly. In contrast, voltammograms for high scan rates, v > 1 V s-1, were governed by some kinds of kinetics judging from the scan rate dependence of peaks. The kinetics is close to that of a ferrocenyl derivative, in which the currents include the capacitive component with negative values. The capacitive one can be identified with the proportionality to the scan rates. The variation of the peak currents with v yielded -200 µF cm-2. This negative value, being associated with the charge transfer reaction, makes cyclic voltammograms deviated downward from the diffusion-controlled behavior, resembling an irreversible reaction of the Butler-Volmer kinetics. Double layer capacitances are generally formed so that the applied electric field may be relaxed. The reduction of hemin forms a dipole coupled with a cation of the salt. The dipole orients from the electrode to the bulk, whereas the solvent dipoles orients in the opposite direction. Therefore, the capacitance is observed negatively. The capacitance determined by ac impedance took also negative values when the applied dc potential was only in the potential domain for the charge transfer. These complications can be avoided in electrocatalysis by use of such slow voltammetry as scan rates of 0.1 V s-1 and ac frequency of 0.2 Hz.

Potential Step for Double-Layer Capacitances Obeying the Power Law.

Potential-step chronoamperometry was made at a platinum wire electrode in KCl aqueous solution at the aim of finding the behavior of the power law of the time or the constant phase element for the double-layer (DL) capacitances. The logarithmic current decays linearly with the time shorter than 0.1 ms, and then it obeys the power law in which it has a linear relation with the logarithmic time in the millisecond time domain. The transition from the exponential decay to the power law was expressed theoretically for the model of a series combination of the resistance and the DL capacitance. The expression predicts that the double logarithmic plots of the current-time provide a capacitance value at 1 s from the intercept, independent of the resistance. This prediction was demonstrated experimentally in KCl solutions of which concentrations ranged from 1 mM to 0.5 M. The capacitance can be evaluated simply by chronoamperometry on a 1 s time scale without considering any resistance effect. The capacitance values did not vary with the applied potential.

Adsorption force of polyaniline-coated polystyrene latex particles.

Visible polyaniline-latex particles 13 microm in diameter were used for obtaining a quantitative relationship between the adsorption force and the electroactivity at a platinum electrode. An optical cell equipped with wire electrodes was filled with the suspension in hydrochloric acid. When electrode potential was switched between the oxidized and the reduced domains, some adsorbed particles showed color change owing to the electroactivity. The numbers of electroactive and the inactive particles in the suspension were counted, including poly(N-vinylpyrrolidone) (PVP). The ratio of the numbers was proportional to the concentration of PVP, as it was in equilibrium. The adsorbed particles were desorbed mechanically by forced flow. The numbers of the desorbed particles did not decrease with an increase in the flow velocity until threshold values. The threshold value for the electroactive particle was 10 times larger than that for the inactive ones, corresponding to 10 times larger adsorption energy of the electroactive particles than of the inactive ones. The adsorption stress was evaluated from the removal of the electropolymerized polyaniline film from the electrode. Then the adsorption area of the particle was estimated.

Garcinone B reduces prostaglandin E2 release and NF-kappaB-mediated transcription in C6 rat glioma cells.

In the course of our survey of natural compounds inhibiting prostaglandin E2 release and/or lipopolysaccharide (LPS)-induced transcriptional stimulation via NF-kappaB, a central regulator of inflammatory genes, from natural resources, we found garcinone B, a xanthone from callus tissue culture of Hypericum patulum, as a compound with such pharmacological activities, that is a derivative of gamma-mangostin which potently inhibits COX-1 and COX-2 activities to reduce PGE2 release from C6 rat glioma cells, and inhibits IKK activity to prevent NF-kappaB-dependent COX-2 gene transcription. Garcinone B, to a lesser extent, reduced A23187-induced increase in prostaglandin E2 release than gamma-mangostin and its structurally related compound, patulone, in C6 cells. This compound also prevented LPS-induced stimulation of NF-kappaB-dependent transcription. These results suggest that garcinone B becomes a unique pharmacological tool to investigate intracellular signaling pathways involved in inflammation.

Molecular numbers in core and shell: structural dependence of reactivity of alkylcarboxylate-stabilized silver nanoparticles.

Spectroscopic, chemical, thermal, and voltammetric analyses on six kinds of alkylcarboxylate-stabilized silver nanoparticles 4.7 nm in diameter were carried out with an aim to reveal the effect of alkylcarboxylates on the optical, thermal, geometric, and electrochemical properties of the nanoparticles. These nanoparticles are composed of silver atoms and silver alkylcarboxylates having even numbers, m, of carbon atoms from 8 to 18. As a measure of the structure of the nanoparticles, the ratio of the number of silver atoms (nAg) to that of alkylcarboxylates (ns) per nanoparticle was evaluated by means of titration through chemical oxidation, voltammetric currents, and thermal gravimetric analysis. It increased with an increase in m and ranged from 1.3 to 9.8. Properties of the nanoparticle have been exhibited in absorbance of the UV-vis spectra at the point of the proportionality to n(Ag), voltammetric currents of which values were close to the theoretical values at the diffusion of particle itself, and the m-independent kinetic energy of the thermal decomposition and the overpotential of the reduction. They are not observed for the composed species, that is, silver atoms and silver alkylcarboxylate molecules.

Size-distribution of droplets in emulsions by statistical mechanics calculation.

This report is concerned with theoretical demonstration of the spontaneous emulsification which has been observed in a soft contact of nitrobenzene with water without surfactant [K. Aoki, M. Li, J. Chen, T. Nishiumi, Electrochem. Commun. 11 (2009) 239]. The demonstration is based on the model of spherical oil droplets with any size in equilibrium. The droplets are composed of the smallest droplets, the total number of which is given. An assembly of small droplets has larger surface energy than that of large ones because the surface energy is proportional to the surface area. The former has larger configurational entropy than the latter because the number of small droplets is bigger than that of the large ones. Since the free energy is determined by the competition between the surface energy and the entropy, it is not clear which assembly has lower free energy. This question was solved numerically here by statistical mechanics calculation of the size distributions, which contained only a parameter of the surface energy. The results of the computation at small number of droplets were used for deriving approximate equations for extremely large number of droplets. The size distribution was localized both to the smallest and the largest droplets. The diameter of the largest droplet was estimated from the dynamics in which coalescence by diffusion of droplets is disturbed by gravitational convection. The size then predicted was of the order of micrometer, being close to experimental values.

Temperature-dependence of hydrogen oxidation reaction rates and CO-tolerance at carbon-supported Pt, Pt-Co, and Pt-Ru catalysts.

The temperature-dependence of the hydrogen oxidation reaction (HOR) rate was examined at commercial Pt, Pt3Co, PtRu, and PtRu(1.5) nano-sized catalysts (diameter, d = ca. 3 nm) supported on carbon black in 0.1 M HClO4 solution in the presence and absence of carbon monoxide by use of a channel flow electrode at temperatures from 30 to 90 degrees C. It was found that the values of the apparent rate constant k(app) (per real Pt active surface area) for the HOR at these supported catalysts agreed beautifully with those of the corresponding bulk electrodes in the whole temperature range. The dependence of the kinetically controlled current density (jk) on CO coverage at each supported catalyst was also identical to that of the bulk. Hence, no particle size effect was observed on the HOR activity and the CO tolerance, at least, was brought down to d = 3 nm.

Electrically driven motion of an air bubble on hemispherical oil/water interface by three-phase boundary reactions.

Our electrochemical cell consisted of a ferrocene-included hemispherical nitrobenzene (NB) droplet on the glassy carbon (GC) electrode which was immersed in the aqueous solution including sodium sulfate and sodium dodecyl sulfate (SDS). When an air bubble was injected near the boundary between the oil and the aqueous phase, it stayed at the top of the hemisphere on the boundary so that the lower half of the bubble was put in oil and the other half was in water. From the force balance of surface tension and buoyancy of the bubble, the bubble took an energetic minimum at the interface. It sank into the oil phase when ferrocene in the oil was electrochemically oxidized through the GC electrode by the three-phase boundary reaction. The electrochemical reduction caused the bubble to move back toward the aqueous phase. The motion of the bubble was synchronized with the redox reaction of ferrocene. The potential step oxidation showed such a rapid response that the motion could not be attributed to diffusion of ferricenium ion from the three-phase boundary to the bubble. Our idea of explaining the rapidity was the translational motion of the SDS layer along the boundary, which was driven by the difference in the surface concentration of SDS caused by the electrochemical generation of the ferricenium ion. The motion of the SDS layer was demonstrated by the shrinkage of the oil layer spread on the water surface when SDS solution was dropped on the oil layer. The spreading velocity was close to the velocity of propagating the oxidation of ferrocene to the bubble.

Voltammetry of suspensions of hollow particles with ferrocene-immobilized polyallylamine shells.

Redox-active hollow spheres were prepared through extracting a polystyrene core from the latex particle (PSPAAFc) composed of the core and the polyallylamine shell including ferrocenyl carboxylic amide. The suspension of the hollow spheres showed anodic and cathodic voltammetric peaks, which were nearly reversible and diffusion-controlled. The current was 3 times as large as the current for the suspension of the filled PSPAAFc. This value agreed with the theoretical one evaluated from the diameter (1.28 microm), the number of ferrocenyl moieties per particle, 1.2 x 108, by UV spectroscopy, and the diffusion coefficient obtained from the Stokes-Einstein equation. This fact indicates the reaction of the whole loaded charge, in contrast to the partial charge transfer of PSPAAFc. The dynamic flattening motion was observed to support the reaction of the whole charge.

Enhancement of electrochemical activity by small-sizing the vinylferrocene-immobilized polystyrene latex particles.

Voltammetry of vinylferrocene (VFc)-immobilized polystyrene(PS)-based latex particles was carried out in aqueous suspensions by changing the size of latex particles in order to investigate the dependence of the electroactivity of the particles on their size. The anodic peak current was controlled by diffusion of the latex. The voltammetric peak currents increased with an increase in the diameter of PS latex particles for a given analytical concentration of the particles, exhibiting the dependence on 1.5 powers of the diameter of the particles. The increase can be explained in terms of combination of the uniform distribution of VFc in the particle, the partial charge transfer, and the Stokes-Einstein equation for diffusion coefficients. The oxidation of VFc occurs in the restricted domain (0.07 microm) from a contact point of the particle with the electrode. The overall reaction mechanism is diffusion of the particle to the electrode, partial oxidation to VFc+, release of VFc+ from the particle to the solution, and reduction of the released VFc+.

Electrochemical generation of free nitric oxide from nitrite catalyzed by iron meso-tetrakis(4-N-methylpyridiniumyl)porphyrin.

Electrochemical generation of free nitric oxide (NO) from nitrite (NO(2)(-)) catalyzed by iron meso-tetrakis(4-N-methylpyridiniumyl)porphyrin, [Fe(III)(TMPyP)](5+), has been developed in this study. To obtain free NO, a cathodic electrolysis and an anodic electrolysis were performed in two connected flow electrolytic cells in sequence. The flow electrolytic cell upstream was used for cathodic electrolysis, where the solution of [Fe(III)(TMPyP)](5+) and NO(2)(-) was reduced at -0.25 V (vs Ag/AgCl) into [Fe(II)(NO(2)(-))(2)(TMPyP)](2+) and [Fe(II)(NO)(TMPyP)](4+) in sequence. The flow electrolytic cell downstream was utilized for anodic electrolysis, where [Fe(II)(NO)(TMPyP)](4+) formed from the upstream cell was oxidized at +0.40 V (vs Ag/AgCl) into [Fe(III)(TMPyP)](5+) and free NO. Finally, NO was bubbled out from anodic electrolyte by argon gas. The mechanism and the optimum conditions for electrochemical generation of NO from NO(2)(-) catalyzed by [Fe(III)(TMPyP)](5+) were studied in detail by voltammetric and spectroelectrochemical methods.

Diffusive-convective transport into a porous membrane. A comparison of theory and experiment using scanning electrochemical microscopy operated in reverse imaging mode.

Molecule transfer at the interface between a single ion-selective micropore and aqueous solutions is quantitatively investigated using scanning electrochemical microscopy operated in reverse imaging mode (SECM-RIM). Accumulation of two electroactive solute molecules, acetaminophen and ferrocenylmethyltrimethylammonium, at the pore/solution interface is observed when an electrical current is passed through the pore. Slow interfacial transfer of solute relative to the solvent as the solution is driven across the membrane by electroosmosis is responsible for solute accumulation. A theoretical expression for the concentration distribution of solute molecules above an individual pore opening is obtained by analytical solution of the convective-diffusive flux equation. The fluid velocity through the pore at constant electroosmotic force is determined by fitting the theoretical expression to SECM-RIM concentration profiles and is found, as anticipated, to be independent of the solute species and the bulk solute concentration. The results provide a theoretical basis for the SECM-RIM imaging of biological membranes as well as a general method for characterizing interfacial molecule/ion transfer kinetics.