The electrochemical (EC) behavior of mechanically exfoliated graphene and highly oriented pyrolytic graphite (HOPG) is studied at high spatial resolution in aqueous solutions using Ru(NH 3 ) 6 3+/2+ as a redox probe whose standard potential sits close to the intrinsic Fermi level of graphene and graphite. By coupling scanning electrochemical cell microscopy (SECCM)

ABSTRACT:There is considerable interest in understanding the interaction and activity of single entities, such as (electro)catalytic nanoparticles (NPs), with (electrode) surfaces. Through the use of a high bandwidth, high signal/noise measurement system, NP impacts on an electrode surface are detected and analyzed in unprecedented detail, revealing considerable new mechanistic information on the process. Taking the electrocatalytic oxidation of H2O2 at ruthenium oxide (RuOx) NPs as an example, the rise time of currenttime transients for NP impacts is consistent with a hydrodynamic trapping model for the arrival of a NP with a distancedependent NP diffusion-coefficient. NP release from the electrode appears to be aided by propulsion from the electrocatalytic reaction at the NP. High frequency NP impacts, orders of magnitude larger than can be accounted for by a single pass diffusive flux of NPs, are observed that indicate the repetitive trapping and release of an individual NP that has not previously recognized. The experiments and models described could readily be applied to other systems and serve as a powerful platform for detailed analysis of NP impacts.An important frontier in electrochemistry is measuring the behavior of individual nano-entities such as nanoparticles (NPs), nanowires and nanorods and relating this to other properties such as size, structure and electronic characteristics, so as to develop fundamental understanding and rational applications. 1-3 An interesting approach for observing the electrochemical properties of catalytic NPs is to monitor their impact (or landing) from solution onto a collector electrode, as introduced by Bard et al.,4,5 and developed by several groups. [6][7][8][9][10][11][12] In order to resolve such impacts, the use of a small-sized ultramicroelectrode (UME) is mandatory to reduce both background currents and the impact frequency. To enhance the impact signal to background current, electrode surfaces have been modified with Hg or Bi 7 and borondoped diamond 12 has also been used as an UME material. Alternatively, scanning electrochemical cell microscopy (SECCM) functioning as an ultramicro-electrochemical cell system offers particularly low background currents by reducing the area of the collector electrode, as well as offering the widest range of support electrodes. This is because the electrochemical cell is formed by meniscus confinement, rather than electrode encapsulation (Figure 1). 13 Despite these innovations, detailed analysis of the form of the current-time profile which is the primary signal for the landing (and detachment) of a single NP on an electrode has not yet been forthcoming, but would represent a huge advance towards understanding the impact process. Herein, we are able to analyze this process as never before and deduce key information on the NP arrival and release process from individual impact transients. Moreover, we show that impact frequencies can be orders of magnitude higher than expected based on single pass diffusion due to the repetitiv...

A simple method that uses graphene to fabricate nanotopographic substrata was reported for stem cell engineering. Graphene-incorporated chitosan substrata promoted adhesion and differentiation of human mesenchymal stem cells (hMSCs). In addition, we proposed that nanotopographic cues of the substrata could enhance cell-cell and cell-material interactions for promoting functions of hMSCs.

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[Purpose] This study examined the effects of various dual task gait training methods (motor dual task gait training, cognitive dual task gait training, and motor and cognitive dual task gait training) on the balance and gait abilities of chronic stroke patients. [Subjects and Methods] Thirty-three outpatients performed dual task gait training for 30 minutes per day, three times a week, for eight weeks from June to August, 2012. Balance ability was measured pre-and posttest using the stability test index, the weight distribution index, the functional reach test, the timed up and go test, and the four square step test. Gait ability was measured by the 10 m walk test and a 6 min walk test before and after the training. The paired t-test was used to compare measurements before and after training within each group, and ANOVA was used to compare measurements before and after training among the groups. [Results] Comparisons within each group indicated significant differences in all variables between before and after the training in all three groups. Comparison between the groups showed that the greatest improvements were seen in all tests, except for the timed up and go test, following motor and cognitive dual task gait training. [Conclusion] In a real walking environment, the motor and cognitive dual task gait training was more effective at improving the balance and gait abilities of chronic stroke patients than either the motor dual task gait training or the cognitive dual task gait training alone.

The mechanism and kinetics of the electrochemical nucleation and growth of Pd nanoparticles (NPs) on carbon electrodes have been investigated using a microscale meniscus cell on both highly oriented pyrolytic graphite and a carbon coated transmission electron microscopy (TEM) grid. Using a microscale meniscus cell, it is possible to monitor the initial stage of electrodeposition electrochemically, while the ability to measure directly on a TEM grid allows subsequent high resolution microscopy characterization which provides detailed nanoscopic and kinetic information. TEM analysis clearly shows that Pd is electrodeposited in the form of NPs (approximately 1 − 2 nm diameter) that aggregate into extensive nanocrystaltype structures comprised of NPs. This gives rise to a high NP density. This mechanism is shown to be consistent with double potential step chronoamperometry measurements on HOPG, where a forward step generates electrodeposited Pd and the reverse step oxidizes the surface of the electrodeposited Pd to Pd oxide. The charge passed in these transients can be used to estimate the amounts of NPs electrodeposited and their size. Good agreement is found between the electrochemically determined parameters and the microscopy measurements. A model for electrodeposition based on the nucleation of NPs that aggregate to form stable structures isproposed that is used to analyze data and extract kinetics. This simple model reveals considerable information on the NP nucleation rate, the importance of aggregation in the deposition process and quantitative values for the aggregation rate.