S1
Charge Separation in
Ruthenium-Quencher Conjugates
bound to DNA
Katherine E. Augustyn, E.D.A. Stemp†,
and Jacqueline K. Barton*
Division of Chemistry and Chemical Engineering
California Institute of Technology,
Pasadena, California 91125
E-mail: jkbarton@caltech.edu
† Department of Physical Sciences, Mt. Saint Mary’s College, Los Angeles, CA 90049.
* Author to whom correspondence should be addressed
S2
Figure S1.
Electrospray ionization mass spectrum of [{Ru(phen)(dppz)(bpy’-
his)}{Ru(NH
3
)
5
}]
5+
(
A
) and simulated mass spectrum of a compound with the same
chemical formula as [{Ru(phen)(dppz)(bpy’-his)}{Ru(NH
3
)
5
}]
5+
(
B
).
S3
Figure S2.
Reversed-phase HPLC chromatograms monitoring at 450 nm for the three
complexes used in this study are depicted in
A
. The two isomers of
[{Ru(phen)(dppz)(bpy’-his)}{Ru(NH
3
)
5
}]
5+
elute first (bottom trace),
followed by the two isomers of [Ru(phen)(dppz)(bpy’-his)]
2+
(middle
trace) while the two isomers of [Ru(phen)(dppz)(bpy’)]
2+
elute last (top
trace). The absorbance spectra of these complexes are shown in
B
with
analogous positioning as in
A
.
S4
Figure S3
.
Effect of 442 nm irradiation on [{Ru(phen)(dppz)(bpy’-
his)}{Ru(NH
3
)
5
}]
5+
. A plot of the intensity at 650 nm as a function of
irradiation at 442 nm is shown in
A
for the complex in acetonitrile (open
circles) and in 1 mM poly d(AT) in 10 mM sodium phosphate, 50 mM
NaCl, pH 7 (open triangles). HPLC chromatogram of the complex in
acetonitrile following 530 minutes of irradiation at 442 nm is shown as the
middle trace in
B
. [{Ru(phen)(dppz)(bpy’-his)}{Ru(NH
3
)
5
}]
5+
(bottom
trace) and [Ru(phen)(dppz)(bpy’-his)]
2+
(top trace) are shown for
comparison.
S5
Figure S4
.
Electrochemical profiles for oxidation of [Ru(phen)(dppz)(bpy)]
2+
(
A
) and
[Ru(phen)(dppz)(bpy’-his)]
2+
(
B
). Samples were measured in acetonitrile
with 0.1 M tetrabutylammonium hexafluorophosphate. See Experimental.
S6
Table S1
.
DNA sequences and extinction coefficients
DNA Sequence (5’-3’)
260
(M
-1
cm
-1
)
A
ATACGGCTGACTACGGCTCGT
197200
B
ACGAGCCGTAGTCAGCCGTAT
205700
G2-A ATAC
CP
G
GCTGACTACGGCTCGT
197200
G2-B ACGAGCCGTAGTCAGCCGTAT
205700
C1-A ATACGG
CP
C
TGACTACGGCTCGT
197200
C1-B ACGAGCCGTAGTCAGCCGTAT
205700