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desoxyribonucleic acid
Alexander A. Voityuk, Joshua Jortner, M. Bixon, and Notker Rösch
Citation: The Journal of Chemical Physics 114, 5614 (2001); doi: 10.1063/1.1352035
View online: http://dx.doi.org/10.1063/1.1352035
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Combined density functional theory and Landauer approach for hole transfer in DNA along classical molecular
dynamics trajectories
J. Chem. Phys. 130, 215104 (2009); 10.1063/1.3146905
A partially incoherent rate theory of long-range charge transfer in deoxyribose nucleic acid
J. Chem. Phys. 117, 4578 (2002); 10.1063/1.1497162
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JOURNAL OF CHEMICAL PHYSICS VOLUME 114, NUMBER 13 1 APRIL 2001
using the two-state model25 for charge transfer. In what fol- TABLE I. Electronic coupling matrix elements 共in eV兲 for hole-transfer
between two nucleobases in the regular structure of DNA calculated using
lows, we shall denote intrastrand nucleobases
HF/6-31G*.
5 ⬘ – B1 – B2 – 3 ⬘ as B1 – B2 ; the base of the opposite strand
complementary to Bi will be referred as bi 共see Scheme A兲 Intrastranda Interstrand
TABLE II. Matrix elements V for hole transfer in DNA. Comparison between V values for two Watson–Crick
pairs with the corresponding nucleobases pair, and the superexchange model 共all in eV兲.
Corresponding Superexchange
Two Watson–Crick pairs V 关WCP兴a purine pairb V(B1 :B2) c modeld V S
occupied MOs following at energies, HOMO⫺2 and bases, and 共iii兲 one electron energies from the present self-
HOMO⫺3, are localized on pyrimidine nucleobases. consistent field 共SCF兲 calculations. The data of our semi-
The resulting coupling matrix elements for hole transfer empirical calculations15 will be used throughout the article
between purine bases within all dimer duplexes are collected unless explicitly mentioned otherwise. According to that es-
in Table II. For comparison, the matrix elements for purine– timate, ⌬E GC⫽1.6 eV and ⌬E AT⫽0.8 eV. The superex-
purine two-base couplings 共both intra- and interstrand con- change correction contains the matrix element V共B⫽b兲 for
figuration兲 are also presented. Formally, the two-base sys- the 共GC兲 pair: this coupling matrix element is quite large.
tems can be generated from the corresponding duplexes by The superexchange corrections determined by the small in-
dropping the two pyrimidine bases; the atomic coordinates of terstrand coupling 共Table II兲 contribute only 1%–3% in Eq.
the purine bases remain unchanged. Our methodology for the 共1兲. We assert that hole transfer within the dimer duplexes
analysis of the coupling between WCPs rests on the compari- 关共GC兲, 共GC兲兴 and 关共AT兲, 共AT兲兴 is dominated by direct intras-
son to the direct coupling between the corresponding bases trand coupling, i.e. G–G for 关共GC兲, 共GC兲兴 and A–A for
and on the consideration of a superexchange correction to the 关共AT兲, 共AT兲兴.
coupling between WCPs. The preceding discussion shows that the superexchange
First, let us consider the systems with two identical model in combination with electron coupling matrix ele-
Watson–Crick pairs where the purine bases belong to the ments of two-base models is rather successful. Yet, a critical
same strand. The matrix elements for 关共GC兲, 共GC兲兴 and remark on this procedure of interpreting our quantum chemi-
关共AT兲, 共AT兲兴 are calculated at 0.093 and 0.026 eV, respec- cal results of complex models by Eq. 共1兲 is appropriate. It
tively. These values are close 共within 10%兲 to the hole- relates to the fact that all our quantum chemical results for
transfer matrix elements calculated for the intrastrand inter- the coupling matrix elements are derived from energy split-
actions G–G and A–A which were estimated as 0.084 and tings and thus yield only absolute values. For estimating
0.030 eV, respectively 共Table II兲. The proximity of the nu- electron transfer rates this is not a restriction since rates de-
merical results for the coupling between these two WCPs pend on the square of the coupling matrix element between
and the intrastrand base–base interactions can be readily ra- initial and final states only. On the other hand, application of
tionalized by expressing the coupling between WCPs in Eq. 共1兲 关or of Eqs. 共2兲 and 共3兲, see below兴 requires knowl-
terms of direct coupling and a superexchange correction. edge of the relative signs of the various two-base coupling
Thus for the coupling within the systems 关共GC兲, 共GC兲兴 and elements which we have chosen such that the superexchange
关共AT兲, 共AT兲兴 we obtain the superexchange model result model results fit best with the quantum chemical results of
V s 关共 Bb兲 , 共 Bb兲兴 ⫽V 共 B – B 兲 ⫹V 共 B⫽b 兲 兵 V 共 b/B 兲 the complex models. Therefore, our choice of signs rests on
the assumption that the superexchange-based perturbation
⫹V 共 b \ B 兲 其 /⌬E Bb , 共1兲 analysis is valid, and thus agreement with individual quan-
where B, b⫽G,C or B, b⫽A,T, and ⌬E Bb is the energy gap tum chemical results cannot be taken as a confirmation of
for hole transfer from B to b. Different approaches may be such analysis. However, the overall success of our approach
used for estimating this energy gap: 共i兲 experimental redox lends support to our strategy.
potentials for nucleobases in a polar solvent 共see below兲, 共ii兲 Exchange of nucleobases within the first pair,
results of semiempirical calculations on DNA fragments15 关 共GC兲,共GC兲兴 → 关 共CG兲,共GC兲兴 , or the second pair,
that account for the stacking interaction between nucleo- 关 共GC兲,共GC兲兴 → 关 共GC兲,共CG兲兴 , leads to two new systems,
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J. Chem. Phys., Vol. 114, No. 13, 1 April 2001 Electronic coupling between Watson–Crick pairs 5617
where the guanine moieties belong to distinct strands. There- lated coupling of 0.055 eV. Then, the results corrected by the
fore, the first-order contribution to matrix elements of the superexchange term are in reasonable agreement with the
two systems is determined by the direct interstrand interac- calculated couplings for the full model of two WCPs. While
tion between the guanine units. Again, we express the cou- the A/A and AA base couplings differ markedly, the cou-
pling for the systems 关共GC兲, 共CG兲兴 and 关共CG兲, 共GC兲兴 in terms pling strengths for 关共AT兲, 共TA兲兴 and for 关共TA兲, 共AT兲兴 are
of direct and superexchange interactions, rather similar due to large canceling contributions of the su-
perexchange interactions.
V S 关共 Bb兲 , 共 bB兲兴 ⫽V 共 B/B兲 ⫹2V 共 Bvb兲 V 共 B–b兲 /⌬E Bb ,
We have already seen that the strength of the electronic
共2a兲
coupling for hole transfer can depend crucially on the order-
V S 关共 bB兲 , 共 Bb兲兴 ⫽V 共 B\B兲 ⫹2V 共 Bvb兲 V 共 B–b兲 /⌬E Bb , ing of two pairs in DNA, e.g., 关共GC兲, 共CG兲兴 and 关共CG兲,
共2b兲 共GC兲兴 共Table II兲. As a further example, we consider hole
where B, b⫽G,C and the energy gaps ⌬E Bb were obtained transfer between G and A in the systems 关共GC兲, 共AT兲兴 and
previously.15 From Eq. 共2兲 we infer that the superexchange 关共AT兲, 共GC兲兴, where the purine bases belong to the same
correction terms now involve moderately large intrastrand strand. We express again the coupling for 关共GC兲, 共AT兲兴 and
base–base coupling, with these corrections amounting to 关共AT兲, 共GC兲兴 in terms of direct and superexchange interac-
10%-30% 共Table II兲. The coupling between these WCPs ex- tions
hibits a configurational asymmetry, with quite different val- V S 关共 B1 ,b1兲 , 共 B2b2兲兴 ⫽V 关 B1 –B2兴
ues of 0.022 eV for 关共GC兲, 共CG兲兴 and 0.078 eV for 关共CG兲,
共GC兲兴 共Table II兲. Let us compare these results to those cal- ⫹V 共 B1vb1兲 V 共 b1B2兲 /⌬E B1b1
culated for the superexchange model 共Table II兲. For 关共GC兲,
共CG兲兴 Eq. 共2兲 gives a direct interstrand contribution of 0.019 ⫹V 共 B2vb2兲 V 共 B1 /b2兲 /⌬E B2b2 ,
eV and a value of 0.026 eV with the superexchange correc- 共3兲
tion, compared with the result of 0.022 for the WC pair
calculation. The value of 0.078 eV for 关共CG兲, 共GC兲兴 is higher where B1, b1⫽G, C and B2, b2⫽A, T, or B1, b1⫽A, T and
than the direct interstrand G/G contribution of 0.043 eV and B2, b2⫽G, C, while ⌬E B1b1 and ⌬E B2b2 represent the appro-
the superexchange corrected contribution, Eq. 共2兲, of 0.046 priate energy gaps. The direct couplings G–A or A–G, as
eV 共Table II兲. From the comparison of the electronic cou- well as the perturbative results from Eq. 共3兲, i.e., 0.090 eV
pling in 关共GC兲, 共CG兲兴 and 关共CG兲, 共GC兲兴 we infer that the for 关共GC兲, 共AT兲兴 and 0.043 eV for 关共AT兲, 共GC兲兴 共Table II兲,
matrix elements of related systems are very sensitive to the exhibit the same trend of large directional asymmetry as the
order of a WCP in the model. The guanine–guanine inter- calculated couplings between WCP. Finally, for the system
strand coupling depends crucially on the mutual orientation 关共GC兲, 共T,A兲兴 we find a large superexchange correction
of these bases, i.e., GG or G/G, in DNA. To check whether 共30%兲 for the direct interstrand G/A coupling, with the per-
the computational results are reasonably stable with respect turbation expansion resulting in a coupling of 0.029 eV, in
to the basis set used we repeated the calculation on 关共GC兲, good agreement with the calculation 共0.026 eV兲 of the cou-
共CG兲兴 using the very flexible basis set 6-311⫹⫹G** which pling between WCPs 共Table II兲. The perturbative superex-
contains diffuse exponents and polarization functions also on change correction is problematic for the system 关共TA兲,
hydrogen atoms. The calculated matrix element of 0.025 eV 共GC兲兴, where the direct coupling between the two purine
is similar to the value of 0.022 eV obtained within the stan- bases is very small (4⫻10⫺3 eV) and the superexchange
dard 6-31G* basis set, yet the computational effort differs by correction gives 30% of the coupling between the WCP.
a factor of 40. From these results and analysis of the matrix elements
Next, we compare the electronic coupling matrix ele- for hole transfer between neighboring WCP we conclude the
ments for the structures 关共AT兲, 共TA兲兴 and 关共TA兲, 共AT兲兴 following.
where the adenine bases belong to opposite DNA strands 共1兲 The purine–purine electronic coupling provides the
with the results of two-base models for the orientations AA dominant contribution to the hole transfer matrix elements,
and A/A 共Table II兲. These two couplings can be expressed in irrespective whether the nucleobases belong to the same or to
terms of Eqs. 共2a兲 and 共2b兲 with B,b⫽A,T. For the systems opposite strands.
关共AT兲, 共TA兲兴 and 关共TA兲, 共AT兲兴 the direct contribution to the 共2兲 Superexchange corrections are large 共10%–30%兲 for
interaction involves the interstrand AA and A/A couplings, interstrand hole transfer between purines within dimer du-
respectively, whose magnitude is larger than that for the in- plexes, where the superexchange corrections are determined
trastrand A–A pair coupling 共Table I兲. On the other hand, the by the 共large兲 intrastrand couplings. For intrastrand hole
superexchange correction terms 关共AT兲, 共TA兲兴 and 关共TA兲, transfer between the purines, superexchange corrections are
共AT兲兴 共Table II兲, which involve the contribution of intras- small 共1%–3%兲, as the correction is determined by the
trand couplings, are quite large 共10%–30%兲. Bearing in 共mostly small兲 interstrand couplings.
mind that we do not calculate the sign of the coupling matrix 共3兲 The couplings exhibit a marked base order specific-
elements 共both between WCP and between bases兲, we assert ity, which can be traced to the specificity of the coupling
that for 关共AT兲, 共TA兲兴 a positive superexchange correction between the purines. While the electronic coupling between
共with ⌬E AT⫽0.8 eV) applies in Eq. 共2兲, resulting in a calcu- 共GC兲 pairs with the guanines being located on the same
lated coupling of 0.043 eV, while for 关共TA兲, 共AT兲兴, a nega- strand is significantly larger than the matrix elements for
tive superexchange correction in Eq. 共2兲 results in a calcu- complexes, where the guanines are located on different
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5618 J. Chem. Phys., Vol. 114, No. 13, 1 April 2001 Voityuk et al.
TABLE III. Electronic coupling matrix elements 共in cm⫺1兲 for hole transfer the role of through-space interaction between the guanines in
between guanine bases in GAG and GTG trimer duplexes. these trimers. To this end, we calculated the duplex G – G,
Calculation on Direct and super- obtained by removing the intermediate AT pair from the
Duplex complete model Superexchange V S a exchange V ⬘S b complexes GAG or GTG. The resulting ‘‘through-space’’
electronic coupling is calculated to V(G – G)⫽0.0046 eV.
GAG 163 121 158共⫹兲, 84共⫺兲
GTG 48 91 54共⫺兲, 128共⫹兲 This result is somewhat smaller than the matrix elements
computed for the trimer GTG, and comparable to the matrix
a
Equation 共4兲. elements for GAG. Again, this value is rather stable with
b
Equation 共5兲.
respect to the basis set used; with the flexible basis set
6-311⫹G* the G – G coupling is calculated to 0.0050 eV. In
strands. The opposite trend is found for 共AT兲 pairs. This any case, the contributions of the through-space G – G cou-
distinction can be rationalized in terms of the extraordinary pling in the trimer duplexes considered here is substantial
large interstrand A/A and AA couplings. and this direct coupling has to be incorporated in the super-
共4兲 Hole transfer can exhibit a pronounced directional exchange expressions. Thus, Eqs. 共4a兲 and 共4b兲 have now to
asymmetry. For instance, the coupling matrix in 关共GC兲, be modified to read
共AT兲兴 is about five times larger than that of 关共AT兲, 共GC兲兴; in
both systems G and A are in the same strand with the orien- V S⬘ 共 GTG兲 ⫽V 共 G – G兲 ⫹V s 共 GTG兲 , 共5a兲
tations 5 ⬘ – GA– 3 ⬘ and 3 ⬘ – AG– 5 ⬘ , respectively. On the
other hand, very similar electronic couplings are found for V S⬘ 共 GAG兲 ⫽V 共 G – G兲 ⫹V s 共 GAG兲 . 共5b兲
the systems 关共GC兲, 共TA兲兴 and 关共CG兲, 共AT兲兴 with distinct in-
terstrand orientation of G and A. The relative signs of the direct V(G – G) and of the superex-
共5兲 The matrix elements for hole transfer between WCPs change contributions are not determined from our calcula-
can be evaluated in most cases 共except for 关共TA兲, 共GC兲兴兲 tions. In Table III we presented the estimates of V ⬘S , Eqs.
from the perturbative superexchange expressions, Eqs. 共1兲– 共5a兲 and 共5b兲, when the direct and superexchange contribu-
共3兲, with an accuracy of 40%. This implies an uncertainty of tions are of the same sign 关denoted by 共⫹兲兴 and of opposite
about a numerical factor of 2 in the corresponding rates. This signs 关denoted by 共⫺兲兴. It appears that good agreement can
conclusion is significant for the transferability of the infor- be accomplished between the complete calculation for the
mation obtained for the electronic matrix elements between duplex trimer and the direct plus superexchange coupling
nucleobases to estimate the electronic couplings for hole scheme, Eq. 共5兲, with an appropriate 共but admittedly arbi-
transfer 共hopping兲 between guanines in large systems. trary兲 choice of the relative signs of the two contributions in
Eq. 共5兲.
B. The trimer duplexes GAG and GTG From these data and analysis we conclude that:
共1兲 The difference between the coupling matrix elements
Our calculations on the trimer duplexes GAG and GTG of the trimer duplexes GAG and GTG originates from cumu-
yield hole transfer matrix elements between the guanines of lative contributions to the superexchange terms comprising
0.020 and 0.006 eV, respectively. It is instructive to express 共i兲 the base–base intrastrand interactions, which are consid-
these coupling matrix elements for the trimer duplexes by erably larger for the GTG duplex 关V(G–T)V(T–G)⫽1.2
superexchange expressions based on the two-nucleobase ⫻10⫺2 eV2, while V(G–A)V(A–G)⫽4.4⫻10⫺3 eV2兴, and
model. The leading superexchange contributions are 共ii兲 the energy gaps, which are considerably lower for GAG
V S 共 GTG兲 ⫽V 共 G–T兲 V 共 T–G兲 /⌬E GT , 共4a兲 (⌬E GA⬇0.3 eV and ⌬E GT⬇1.0 eV), which increase
V s (GAG) relative to V s (GTG).
V S 共 GAG兲 ⫽V 共 G–A兲 V 共 A–G兲 /⌬E GA , 共4b兲 共2兲 The mutually compensating contributions 共i兲 and 共ii兲
where the intrastrand couplings V(B1 –B2) are taken from 关see point 共1兲 above兴 manifest the influence of the interven-
Table I and the energy gaps are ⌬E GT⫽E(GT⫹G) ing pair 共i.e., the ‘‘through-pair’’ interaction兲 on the matrix
⫺E(XG⫹A)⫽1.0 eV and ⌬E GA⫽E(GA⫹G)⫺E(XG⫹A) element; concurrently, the ‘‘through-space’’ interaction of
⫽0.30 eV, as estimated using our energy data for trimer the guanines in the trimer duplexes is significant.
duplexes.15 Additional superexchange corrections to Eqs. 共3兲 The ‘‘through-space’’ G – G interaction 共37 cm⫺1 at
共4a兲 and 共4b兲 involving interstrand couplings 关e.g., R GG⫽6.76 Å) is large. It appears that for hole transfer in
V(G/T)V(TG)/⌬E GT to Eq. 共4b兲兴 are small 共⬃1 cm⫺1兲 and DNA, in contrast to that for charge transfer in proteins,3 the
can be safely neglected. In Table III we compare the super- ‘‘through-space’’ electronic coupling is important. This
exchange results, which are confronted with the direct calcu- value of V(G – G), together with the intrastrand nearest-
lations of the coupling matrix elements, where the agreement neighbor value of 677 cm⫺1 at R GG⫽3.38 Å, implies that
is within a numerical factor of 2. One source of the discrep- this matrix element for GG coupling 共at the DNA regular
ancy involves the contribution of the direct G–G ‘‘through- configuration兲 decreases exponentially, i.e., V(G–G)⬀exp
space’’ coupling interaction which we will consider next. (⫺bRGG) with b⫽0.86 Å ⫺1 . This value of b is considerably
Comparing the matrix elements for GAG and GTG one im- lower than the value of b⫽1.58 Å ⫺1 inferred in our study24
mediately concludes that the intervening Watson–Crick pair for parallel nucleobases, over a small R range, possibly re-
determines the efficiency of the hole transfer between gua- flecting the angular dependence of the electronic coupling
nines. Yet, there remains the interesting question concerning matrix elements.
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J. Chem. Phys., Vol. 114, No. 13, 1 April 2001 Electronic coupling between Watson–Crick pairs 5619
共4兲 The electronic coupling matrix elements in the trimer electronic coupling matrix elements reported herein and the
duplexes originate from a delicate balance between the cou- sparse experimental data on the hole electronic coupling
plings and energetic components of the superexchange term which emerge from rates for hole injection, hopping, and
and between the superexchange ‘‘through-pair’’ and direct trapping.8,9,21,22 For an elementary hole transfer process in
‘‘through-space’’ interactions. In particular, our ignorance of the DNA duplex
the relative signs of these ‘‘through-pair’’ and ‘‘through-
k
space’’ contributions implies that reliable estimates of the
d ⫹ B1B2B3 ...BN a → dB1B2B3 ...BN a ⫹ , 共6兲
hole transfer matrix elements 共in the idealized duplex in the
gas phase兲 should rest on a complete calculation for the su- where d is the hole donor, a is the acceptor, and B1 ,B2 ...BN
perstructure of the trimer duplex, while the superexchange are the intervening nucleobases of the bridge, the semiempir-
contribution will result only in a semiquantitative estimate ical superexchange electronic coupling matrix is18
共see Table III兲 of these electronic coupling terms.
V⫽ v共 d,B1兲v共 BN ,a 兲
IV. CONCLUDING REMARKS N⫺1
very crude estimate for G(T) m G results in V (S) ⬃197, 47, 12 共AT兲 pair.8,9,21,22,23,34 Thus far, no experimental evidence for
cm⫺1 for m⫽1, 2, 3. The latter value (m⫽3) is in qualitative the specificity of T vs A in mediating intrastrand hole hop-
agreement with Harriman’s estimate33 of the electronic cou- ping was recorded.
pling of 4 cm⫺1 for intercalated d and a with m⫽3. A more
elaborate comparison requires the evaluation of donor- ACKNOWLEDGMENTS
nucleobase electronic matrix elements in the systems studied This work was supported by the Deutsche Forschungs-
by Harriman.33 gemeinschaft 共SFB 377兲, the Volkswagen Foundation, and
the Fonds der Chemischen Industrie.
B. Distance dependence of the electronic coupling
1
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4
E. D. Stemp, M. R. Arkin, and K. J. Barton, J. Am. Chem. Soc. 119, 2921
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17
hole donors are not yet available, one can consider the quan- I. Saito, T. Nakamura, and K. Nakatani, J. Am. Chem. Soc. 122, 3001
共2000兲.
titative information on the reduction of the hole hopping, 18
M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 共1999兲.
trapping, or recombination rates upon the increase of the size 19
J. Jortner, M. Bixon, T. Langenbacher, and M.-E. Michel-Beyerle, Physica
of the bridge of nucleobases. Provided that the electronic A 95, 12759 共1998兲.
20
couplings obey the empirical exponential distance depen- S. Priyadanshy, S. M. Risser, and D. N. Beratan, J. Phys. Chem. 100,
17678 共1996兲.
dence discussed in Sec. IV B, the reduction factor can be 21
M. Bixon, B. Giese, S. Wessely, T. Langenbacher, M.-E. Michel-Beyerle,
expressed in the form r⫽exp(⫺bRBB), where R BB is the and J. Jortner, Proc. Natl. Acad. Sci. U.S.A. 96, 11713 共1999兲.
nearest-neighbor interbase distance in the bridge. The reduc- 22
M. Bixon and J. Jortner, J. Phys. Chem. B 104, 3906 共2000兲.
23
tion factor of the hole superexchange rate in systems Y. A. Berlin, A. L. Burin, and M. Ratner, J. Phys. Chem. A 104, 443
共2000兲.
5 ⬘ – G(T) m G– 3 ⬘ per addition of an additional T base is r T 24
A. A. Voityuk, N. Rösch, M. Bixon, and J. Jortner, J. Phys. Chem. B 104,
⫽ 关 V(T–T)/⌬E GT兴 2 . Using the energy gap value15 ⌬E GT 9740 共2000兲.
⫽1.3 eV together with the value V(T–T)⫽0.16 eV for the 25
M. D. Newton, Chem. Rev. 91, 767 共1991兲.
26
electronic coupling 共Table I兲, one obtains r T⫽0.015, i.e., the X. J. Lu, M. A. El Hassan, and C. A. Hunter, J. Mol. Biol. 273, 681
共1997兲.
reduction of the rate by a numerical factor of 70 per bridge 27
L. Clowney, S. C. Jain, A. R. Srinivasan, J. Westbrook, W. K. Olson, and
nucleobase. Using the energy gap ⌬E GT (S)
⬇0.6 eV estimated H. W. Berman, J. Am. Chem. Soc. 118, 509 共1996兲.
28
on the basis of experimental redox potentials of the nucleo- For three-dimensional illustrations of the DNA structure, in particular con-
cerning the difference in the spatial orientations of the 5 ⬘ – 5 ⬘ and 3 ⬘ – 3 ⬘
bases in solution results in r T⫽7⫻10⫺2 , i.e., a reduction of
couplings, the reader is referred to textbooks of biochemistry, e.g. 共a兲 V.
the rate by a factor of 15. Similarly, for the system A. Bloomfield, D. M. Crothers, and L. Tinoco, Nucleic Acids. Structures,
5 ⬘ – G(A) m G– 3 ⬘ the reduction factor upon the addition of an Properties, and Functions 共University Science Books, Sausalito, 1999兲;
additional A base is r A⫽ 关 V(A–A)/⌬E GA兴 2 , where the gas 共b兲 D. Voet, J. G. Voet, and Ch. W. Pratt, Fundamentals of Biochemistry
phase energy gap ⌬E GA⫽0.35 eV together with V(A–A) 共Wiley, New York, 1999兲.
29
D. J. Katz and A. A. Stuchebrukhov, J. Chem. Phys. 106, 5658 共1997兲.
⫽0.030 eV results in the low value of r A⫽8⫻10⫺3 . The 30
L. Rodrigues-Monge and S. Larsson, J. Phys. Chem. 100, 6298 共1996兲.
reduction of the effective energy gap due to solvation effects 31
GAUSSIAN98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel,
may increase this value of r A . The experimental results of et al., Gaussian, Inc., Pittsburgh, PA, 1998.
32
S. Larsson, Biochim. Biophys. Acta 294, 1365 共1998兲.
Giese et al. and of Lewis et al. seem to imply that the reduc- 33
A. Harriman, Angew. Chem. Int. Ed. Engl. 38, 945 共1999兲.
tion factors are r T⬇r A⬇0.03– 0.1, i.e. a reduction of the 34
F. D. Lewis, X. Liu, S. E. Miller, R. T. Hayes, and M. R. Wasielewski,
hole hopping rate by a factor of 10–30 upon addition on one Nature 共London兲 406, 51 共2000兲.
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