Interaction of 0-15 eV electrons with DNA: Resonances, diffraction and charge transfer
description
Transcript of Interaction of 0-15 eV electrons with DNA: Resonances, diffraction and charge transfer
Interaction of 0-15 eV electrons with DNA: Resonances, diffraction and
charge transfer
The presented results represent the work of many scientists especially: Marc Michaud Sylwia Ptasinska Badia Boudaiffa Michael Huels Pierre Cloutier Darel Hunting Hassan Adoul-Carime Xiaoning Pan Luc Parenteau Andrew Bass Frederick Martin Yi Zheng Richard Wagner Xifeng Li Michael Sevilla Laurent Caron This work was funded by:
DNA and sub-units
N N
N C6 N
NH2
Guanine
Cytosine
Thymine
Adenine
tetrahydrofuran(THF)
3-hydroxy-tetrahydrofuran
-tetrahydrofurylalcohol
+ H2O
Apparatus for productanalysis
"Electron stimulated desorption of H¯ from thin films of thymine and uracil" M.-A. Hervé du Penhoat et al., J. Chem. Phys. 114, 5755 (2001).
QuadrupoleMass
Spectrometer
Ionizer& Ion Lenses
CustomIon Lenses
Filament
Deflector
ElectronLenses
ElectronGun
Load - Lock
Chamber(Preparation)
Oven
Channeltron
Linear Transfer & Rotation
RotatableShutter
RotatableSampleHolder
MainChamber
GateValve
10 torr-1010 torr-9
0 10 20 30 40 50 60 70 80 90 1000.0
0.2
0.4
0.6
0.8 MDSB
(c)
0
1
2
(b)
Incident Electron Energy (eV)
DSB
0
5
10
(a)
SSB
DN
A S
tran
d B
reak
Yie
ld (
x 10
- 4
) pe
r In
cide
nt E
lect
ron
LEE Damage to Plasmid DNA M.A. Huels et al., J.A.C.S. 125, 4467 ( 2003)
LEE damage to DNA – Intro/Summary• DNA damage induced by LEE below 15 eV occurs principally
by the formation of transient anions of the subunits. The contribution from direct scattering increases with energy.
• Anion ESD yields of: H¯ arises from the bases with a small contribution from the backbone, O¯ from the phosphate group, and OH¯ from a protonated phosphate group. Other anions have been observed.
• Anion ESD yields arise from DEA below 15 eV.
• Two major pathways of LEE reactions in DNA: cleavage of the N-glycosidic bond (base release) and the phosphodiester bond (strand break).
• Phosphodiester bond breaks by C-O bond rather than P-O bond rupture.
• Between 0-5 eV, SSB are produced with a cross section of about E-14 cm2 for 3,000 bp, similar values are found at 10 and 100 eV.
Sub-excitation energy electron damage Sub-excitation energy electron damage to DNAto DNA
Barrios et al J. Phys. Chem. 106, 7991 (2002) - Electron capture by cytosine and transfer to dissociative C-O bond
Li et al JACS 125, 13668 (2003) - Scission of 5’ and 3’ C-O bond by electron attachment. Endothermic by ~0.5 eV
Dablowska et al Eur. Phys. J. D 35, 429 (2005) – Proton transfer mechanism of DNA strand breaks induced by excess electrons.
Gu et al., Nucl. Acids Res. 1-8 (2007) (in press)
[SU¯] (Eo)
[SU] [SU]*DEA+ +
e¯ (Eo) e¯ (E<<Eo)
e¯ce¯t e¯c e¯t
1
2
3SU=subunit base sugar phosphate water
+diffraction
0 1 2 3 4 50
2
4
6
8
10
12
0 1 2 3 4 50
2
4
6
8
10
12
0 1 2 3 4 50
2
4
6
8
10
12
Capture Cross Section Sum
Thymine DEA
Cro
ss S
ectio
n
Electron Energy
Cro
ss S
ectio
n
Electron Energy
Cro
ss S
ectio
n
Electron Energy
Upper curve (Martin et al, Phys. Rev. Lett. 93, 068101 (2004)):From ETS data, sum of capture cross sections for the four bases normalized to the second peak of the DNA damage yield (full squares) and shifted by 0.4 eV.
Lower curve (Denifl et al, Chem.Phys. Lett. 377, 74 (2003)):
DEA cross section from gaseousThymine with no energy shift.
Capture cross section of the bases vs single SB
Electron transfer in DNAElectron transfer in DNA
OH
OO
O
OO
O P OO
OO
O PO
O
OOH
O PO N
N
O
O
N N
N N
O
NH2
NN
O
NH2
guanine
cytosine
thymine
5'
3'
1
23
45
6
X
• LEE induced cleavage reactions greatly impeded next to the abasic site below 6 eV.
• There is a shift of electron transfer to direct attachment from low to high electron energy.
• Electron transfer of LEE occurs from base moiety to the sugar-phosphate backbone in DNA.
Percentage distribution of damage by sites of cleavage, induced by 6, 10 and 15 eV electrons.
*Xp was not detected by HPLC and the yield was considered to lie below the detection limit.Total damage = SB + base release = 100
Yield functions: GCAT Yield functions: GCAT vsvs GCXT GCXT
• For strand break, a resonance shows at around 10 eV.
• Presence of an abasic site greatly decreases the yield of strand break and base release in DNA (three times less).
3 5 7 9 11 13 150
30
60
90
GCAT XCAT GXAT GCXT GCAX
Ion
yiel
d (c
ps)
Electron energy (eV)
OH-
On average 25% decrease for abasic Same results for H- and O- desorption
No diffractionSince OH- and O- originate from the backbone, these anions arise from e-
transfer unless there is a change in the resonance parameters
[base¯] (Eo)
[base] [base]*DEA+ +
e¯ (Eo) e¯ (E<<Eo)
e¯ce¯t e¯c e¯t
1
2
3+diffraction
At higher energies, there is little coherence. Thus, creation of an abasic site has little effect on the branching ratios for electron emission in the continuum or within DNA
At low energies, transfer within DNA becomes much larger, but strongly depends on diffraction and hence is considerably decreased by formation of an abasic site
Neutral particle desorption from a single DNA strand
CN (black squares)OCN and/or H2NCN (white circles)H and H2 desorption also observedRatio CN/OCN is constantResonance structures superimposed in linearly increasing background
0 5 10 15 20 25 3005
101520
dCy6BrU3
Frag
men
ts D
esor
bed
per E
lect
ron
(x10
-3)
Incident Electron Energy (eV)
0
2
4
dCy6T3
0 1 2 3 4 50,0
0,5
1,0
1,5
0 1 2 3 4 50,0
0,5
1,0
1,5
0
2
4
6dCy9
0 1 2 3 4 5
0,0
0,5
1,0
1,5
H. Abdoul Carime et al., Surf. Sci. 451, 102 (2000).
N
NH
R
O
O
X
N
NH
R
O
O
N
NH
R
O
O
N
R
O
O
NHC
O
NHC
+ e - + X - (1)
.
.
CN + OH
OCN + H
(3)
X + e -
+(2)
.
or
Isocyanic acid
Opinion of the presenterOpinion of the presenter
Shape resonances have high cross-section and can lead to DEA Shape resonances have high cross-section and can lead to DEA (the only bond breaking process).(the only bond breaking process).
Electron transfer is high.Electron transfer is high.
Below 3-4 eVBelow 3-4 eV
Above the energy threshold for electronic Above the energy threshold for electronic excitation excitation
Core excited shape resonances have a high cross section for decay Core excited shape resonances have a high cross section for decay into their parent neutral state and direct inelastic scattering may be into their parent neutral state and direct inelastic scattering may be significant. The magnitude of the DEA is not necessarily large significant. The magnitude of the DEA is not necessarily large compared to autoionization.compared to autoionization.
There is little coherent enhancement of the electron wavefunction There is little coherent enhancement of the electron wavefunction at the primary impact energy.at the primary impact energy.Proton transfer has to be re-examined in the Proton transfer has to be re-examined in the context of the present data and hypothesiscontext of the present data and hypothesis
• Are transient negative ions formed within the 0-15 Are transient negative ions formed within the 0-15 eV linked directly to stable anions of the bases or eV linked directly to stable anions of the bases or other SU? other SU?
• If so how?If so how?
Possible mechanismsPossible mechanisms:
1. Vibrational stabilization triggered by the change in DNA configuration by the extra charge. The extra energy (<2eV) of the electron is dispersed in vibrational excitation of DNA and then transfered to the surrounding medium. Does not work for core-excited resonances.
2. Electron-emission decay of a core-excited shape resonance followed by vibrational stabilization.
3. Proton transfer stabilization. Neutralizes the anion charge while leaving a site with a ground state electron.
4. Superinelastic vibrational or electronic electron transfer. [Lu, Bass and Sanche, Phys. Rev. Lett. 88, 17601 (2002)].
4 6 8 10 12 14 16 18 200
25
50
750
25
50
750
25
50
75
(H2O/GCAT)-(GCAT)
H2O
D- from D2O/GCAT
Electron energy (eV)
(c)
(b)
(H2O/GCAT)-(H
2O)
GCATH
- yie
ld (k
cps)
H2O/GCAT
GCAT H
2O
(a)
4 6 8 10 12 14 16 18 20
0
20
40
60
80
100
120
140 16O- from GCAT 16O- from D2O/GCAT
18O- from H218O/GCAT
Ion
yiel
d (c
ps)
Electron energy (eV)
4 6 8 10 12 14 16 18 200
20
40
60
80
100 OH- from GCAT OD- from D2O/GCAT
OH- from H2O/GCAT
18OH- from H218O/GCAT
Ion
yiel
d (c
ps)
Electron energy (eV)
| O | O = P ─ O¯ H+ (O18H) | O |
Site of Site of formationformation