In sampled-current voltammetry (SCV) current transients acquired after stepping the potential along the redox wave of interest are sampled at a fixed time to produce a sigmoidal current-potential curve akin to a pseudo steady state voltammogram. Repeating the sampling for different times yields a family of sampled-current voltammograms, one for each timescale. The concept has been used to describe the current-time-potential relationship at planar electrodes but rarely employed as an electroanalytical method except in normal pulse voltammetry where the chronoamperograms are sampled once to produce a single 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 diffusion at short times to hemispherical diffusion at long times. We also combine microdisk sampled-current voltammetry (MSCV) with a conditioning waveform to produce voltammograms where each data point is recorded with the same electrode history and demonstrate that the waveform is crucial to obtaining reliable sampled-current voltammograms below 100 ms. To facilitate qualitative analysis of the voltammograms we convert the current-potential data recorded at different timescales into a unique sigmoidal curve which clearly highlights kinetic complications. To quantitatively model the MSCVs we derive an analytical expression which accounts for diffusion regime and kinetic parameters.The procedure is validated with the reduction of Ru(NH 3 ) 6 3+ , a model one electron outer sphere process, and applied to the derivation of the kinetic parameters for the reduction of Fe 3+ on Pt microdisks. The methodology reported here is easily implemented on computer controlled electrochemical workstations as a new electroanalytical method to exploit the unique properties of microelectrodes, in particular at short times.

A widely used commercially available system for the investigation of mechanosensitivity applies a biaxial strain field to cells cultured on a compliant silicone substrate membrane stretched over a central post. As well as intended substrate strain, this device also provides a fluid flow environment for the cultured cells. In order to interpret the relevance of experiments using this device to the in vivo and clinical situation, it is essential to characterise both substrate and fluid environments. While previous work has detailed the substrate strain, the fluid shear stresses, to which bone cells are known to be sensitive, are unknown. Therefore, a fluid structure interaction computational fluid dynamics model was constructed, incorporating a finite element technique capable of capturing the contact between the post and the silicone substrate membrane, to the underside of which the pump control pressure was applied. Flow verification experiments using 10-μm-diameter fluorescent microspheres were carried out. Fluid shear stress increased approximately linearly with radius along the on-post substrate membrane, with peak values located close to the post edge. Changes in stimulation frequency and culture medium viscosity effected proportional changes in the magnitude of the fluid shear stress (peak fluid shear stresses varied in the range 0.09-3.5 Pa), with minor effects on temporal and spatial distribution. Good agreement was obtained between predicted and measured radial flow patterns. These results suggest a reinterpretation of previous data obtained using this device to include the potential for a strong role of fluid shear stress in mechanosensitivity.

No abstract