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Transcript
Abs. 739, 205th Meeting, © 2004 The Electrochemical Society, Inc.
Solute-Solvent Interactions from
Impedance Measurements:
Concentration Dependence of DNA
C. V .Krishnan and Merrill Garnett
Garnett McKeen Lab, Inc.
150 Islip Ave., Suite 6, Islip, NY 11751, USA
The unique nature of impedance data
exhibited by palladium lipoic acid (1:1)
complex(1), a chemotherapy agent
developed in our laboratory, prompted us to
investigate in detail the impedance of alkali
chlorides(2) as well as the most important
biological molecule DNA(3). The alkali
chloride data revealed frequency and
potential dependent orientation effects of the
water molecule. DNA impedance data was
subtly dependent on the nature of the alkali
metal ion. This prompted us to study further
the concentration dependence of DNA
impedance without any added electrolyte.
The electrochemical literature data of
nucleic acids(4) are at very low
concentrations of DNA and at negative
potentials of the mercury electrode. The
present investigation was intended to gain
information on the influence of orientation
of solvent molecules, packing, and dopant
ions on the impedance. Therefore
concentrations of 0.1, 1.0, 5.0, and 10.0
mg/mL Calf-Thymus double stranded DNA
(Type I, sodium salt, pH 7.5) were used at
potentials positive enough to produce dopant
ions of mercury.
Typical admittance plots (Figures 1 and 2)
indicate that solvent orientation and DNA
conformation effects are more dominant
(with four peaks) at higher concentrations of
DNA than at lower concentrations (two
peaks). The effects are also enhanced at
lower frequencies. Mott-Schottky plots
indicate dominant p-type behavior. Double
layer capacitance plots exhibit two peaks at
positive potentials. At potentials between
0.2 and 0.3 V, the impedance plot (Figure 3)
and especially the phase angle plot (Figure
4) indicate that the double layer is altered.
Unlike alkali halides, the double layer
changeover potentials seem independent of
DNA concentration. Low frequency effects
are dominant during this changeover of
double layer structure.
For all concentrations of DNA, the
impedance data at -1.5, -1.0, -0.6, -0.3, 0.0,
0.1, 0.2, and 0.3 V could be fitted with the
equivalent electronic circuit of
R(RC)(RC)(RC)(RC).This circuit suggests a
transmission line model for DNA
conductance.
References
1. C.V.Krishnan, and M.Garnett, 1st Spring
Meeting of ISE, Abs. P06, Spain 2003
2. C.V.Krishnan, and M.Garnett, 226th ACS
National Meeting, Abs. Inor. 0028, NY
2003
3. C.V.Krishnan, and M.Garnett, 204th
Meeting of ECS, Abs. 1378, Orlando
2003
4. E.Palecek, M.Fojta, F.Jelen, and V.Vetterl
in Bioelectrochemistry, Vol. 9, Chapter
12, p365, Edited by George S.Wilson,
Wiley-VCH, Weinheim, 2