Nanoparticle-mediated electron transfer across ultrathin self-assembled films.

The electrochemical behavior of arrays of Au nanoparticles assembled on Au electrodes modified by 11-mercaptoundecanoic acid (MUA) and poly-L-lysine (PLYS) was investigated as a function of the particle number density. The self-assembled MUA and PLYS layers formed compact ultrathin films with a low density of defects as examined by scanning tunneling microscopy. The electrostatic adsorption of Au particles of 19 +/- 3 nm on the PLYS layer resulted in randomly distributed arrays in which the particle number density is controlled by the adsorption time. In the absence of the nanoparticles, the dynamics of electron transfer involving the hexacynoferrate redox couple is strongly hindered by the self-assembled film. This effect is primarily associated with a decrease in the electron tunneling probability as the redox couple cannot permeate through the MUA monolayer at the electrode surface. Adsorption of the Au nanoparticles dramatically affects the electron-transfer dynamics even at low particle number density. Cyclic voltammetry and impedance spectroscopy were interpreted in terms of classical models developed for partially blocked surfaces. The analysis shows that the electron transfer across a single particle exhibits the same phenomenological rate constant of electron transfer as for a clean Au surface. The apparent unhindered electron exchange between the nanoparticles and the electrode surface is discussed in terms of established models for electron tunneling across metal-insulator-metal junctions.

Sensitivity and specificity analysis of fringing-field dielectric spectroscopy applied to a multi-layer system modelling the human skin.

The sensitivity and specificity of dielectric spectroscopy for the detection of dielectric changes inside a multi-layered structure is investigated. We focus on providing a base for sensing physiological changes in the human skin, i.e. in the epidermal and dermal layers. The correlation between changes of the human skin's effective permittivity and changes of dielectric parameters and layer thickness of the epidermal and dermal layers is assessed using numerical simulations. Numerical models include fringing-field probes placed directly on a multi-layer model of the skin. The resulting dielectric spectra in the range from 100 kHz up to 100 MHz for different layer parameters and sensor geometries are used for a sensitivity and specificity analysis of this multi-layer system. First, employing a coaxial probe, a sensitivity analysis is performed for specific variations of the parameters of the epidermal and dermal layers. Second, the specificity of this system is analysed based on the roots and corresponding sign changes of the computed dielectric spectra and their first and second derivatives. The transferability of the derived results is shown by a comparison of the dielectric spectra of a coplanar probe and a scaled coaxial probe. Additionally, a comparison of the sensitivity of a coaxial probe and an interdigitated probe as a function of electrode distance is performed. It is found that the sensitivity for detecting changes of dielectric properties in the epidermal and dermal layers strongly depends on frequency. Based on an analysis of the dielectric spectra, changes in the effective dielectric parameters can theoretically be uniquely assigned to specific changes in permittivity and conductivity. However, in practice, measurement uncertainties may degrade the performance of the system.

Towards a realistic dielectric tissue model: a multiscale approach.

In the past, mainly analytical mixing formulas were used for modeling of dielectric properties of biological cells. General drawbacks of such formulas are the restriction to simple shapes and small cellular volume fractions. Assuming cell suspensions or tissues being quasi-periodic the problem size can be reduced to a cubic unit cell containing a single biological cell. Under this assumption numerical, e.g. Finite- Element models of such unit cells provide effective dielectric parameters for the entire tissue or cell suspension. In this work a flexible shape parametrization method allowing for a realistic representation of biological cells is applied to eight different cell types. A non-axisymmetric columnar epithelium cell occurring e.g. in the epidermis is chosen as an example. Numerical simulations of the columnar cell exposed to a time-harmonic electric field are performed for two different, high volume fractions, followed by the extraction of effective dielectric parameters of the bulk material. The simulation results are compared to two analytical approximations for ellipsoidal particles. The results suggest, that the calculation of effective dielectric properties of arbitrarily shaped cells in the frequency range between 100kHz and 1GHz requires at least a numerical cell model.

Validation of human skin models in the MHz region.

The human skin consists of several layers with distinct dielectric properties. Resolving the impact of changes in dielectric parameters of skin layers and predicting them allows for non-invasive sensing in medical diagnosis. So far no complete skin and underlying tissue model is available for this purpose in the MHz range. Focusing on this dispersiondominated frequency region multilayer skin models are investigated: First, containing homogeneous non-dispersive sublayers and second, with sublayers obtained from a three-phase Maxwell-Garnett mixture of shelled cell-like ellipsoids. Both models are numerically simulated using the Finite Element Method, a fringing field sensor on the top of the multilayer system serving as a probe. Furthermore, measurements with the sensor probing skin in vivo are performed. In order to validate the models the uppermost skin layer, the stratum corneum was i) included and ii) removed in models and measurements. It is found that only the Maxwell-Garnett mixture model can qualitatively reproduce the measured dispersion which still occurs without the stratum corneum and consequently, structural features of tissue have to be part of the model.