AVS 57th International Symposium & Exhibition
    In Situ Microscopy and Spectroscopy Topical Conference Wednesday Sessions
       Session IS+BI+AS-WeA

Paper IS+BI+AS-WeA9
Dielectric Constant and Polarization of Biomolecules Determined by Torsional Resonance Nanoimpedance Microscopy

Wednesday, October 20, 2010, 4:40 pm, Room Acoma

Session: In Situ Microscopy/Spectroscopy – Biological Interfaces
Presenter: K. Kathan-Galipeau, University of Pennsylvania
Authors: K. Kathan-Galipeau, University of Pennsylvania
S.U. Nanayakkara, University of Pennsylvania
P.A. O'Brien, University of Pennsylvania
B.M. Discher, University of Pennsylvania
D.A. Bonnell, University of Pennsylvania
Correspondent: Click to Email

We have developed a new technique, torsional resonance nanoimpedance microscopy (TR-NIM), that allows for the measurement of frequency-dependent local transport properties on soft materials. AFM measurements at torsional resonances provide a key advantage: the ability to achieve low-force scanning while maintaining the tip in the near-field. As a result, it is possible to measure impedance between the tip and sample without damaging the sample.

This technique has been used to determine the resistance, capacitance, and dielectric properties of a novel class of biomolecules. These redox active molecules, known as maquettes, consist of dimers and tetramers of alpha helix polypeptides and provide a convenient functional alternative to natural proteins. Maquettes are capable of binding a range of cofactors; this study examines the properties of iron and zinc porphyrins. Maquettes serve as a benchmark for integrating electronics with biologically inspired materials that possess unique characteristics, such as electron-transfer capability, the possibility of gating redox activity, optoelectronic functionality, and nanometer size.

In order to determine the behavior of these functional biomolecules on electrodes, PDMS stamping was used to create stripes that alternate between maquettes and bare graphite. Stamping also allowed us to control the assembly of the redox-active maquettes from multilayers to horizontally oriented monolayers (maquettes laying down) and vertically oriented monolayers (maquettes standing up) by varying the stamping time and the concentration of the maquettes in organic solvents.

Interestingly, we observe that the resistance decreases with increased height of maquettes, which is explained in terms of the configurations of the molecules on the electrode. The dependence of local impedance on exposure to optical radiation revealed an increase in capacitance and decrease in resistance when the maquettes are exposed to 425 nm light. This is true for both zinc and iron porphyrin cofactors. We attribute the decrease in resistance to photoactivated current. The increase in capacitance is due to an increase in the polarizibility of the maquettes.