UV-UV Hole-burning Spectroscopy
of Protonated Adenine Dimer
in a Cold Quadrupole Ion Trap
Hyuk KANG,
Ajou University, Suwon 443-749, Korea
Christophe Jouvet, Claude Dedonder, Géraldine Feraud
Aix-Marseille Université, 13397 Marseille, France
How to Distinguish Neutral Conformers
S1
hνA0-0
hνA0-0 < hνB0-0
hνB0-0
S0
Conformer A
cis-meta-aminophenol
0.319 kcal mol-1
(B3LYP/6-31G**)
Conformer B
trans-meta-aminophenol
Mass-Resolved Conformer-Specific UV Spectrum
S1
UV-UV Double Resonance
UV-UV Hole Burning
hνburn
S0
hνprobe
X
c-3AP
t-3AP
Mass-Resolved Conformer-Specific IR Spectrum
S1
X
IR-UV Double Resonance
IR-UV Hole Burning
Resonant Ion Dip IR (RIDIR)
X
S0
hνt0-0
hνt0-0
c-3AP(NH3)1
X
t-3AP(NH3)1
How to Distinguish Burn and Probe
S1
Mass signal (mV)
0
hνburn
-50
Δt
-100
S0
-150
Burn+Probe
Probe only
-200
-250
21.8
22.0
22.2
22.4
22.6
22.8
Flight time (us)
c-3AP
Each time zero at each laser pulse
t-3AP
hνprobe
UV-UV of Acetaminophen
probe
HB, probe at
33513.18 cm-1
probe
HB, probe at
33515.43 cm-1
FE
33450
33500
33550
33600
wavenumber / cm
W. Y. Sohn, J. S. Kang, S. Y. Lee, and H. Kang, Chem. Phys. Lett. 581, 36 (2013).
33650
-1
33700
33750
Double-Resonance Spectroscopy in QIT?
QIT: Quadrupole Ion Trap
QIT
TOF
MCP
Entrance bias
Probe
Burn
M+
Exit bias
t=0
Time zero at extraction from QIT
Burn signal and probe signal are not distinguishable
UV-UV in QIT with Axial Instability
C. M. Choi, D. H. Choi, J. Heo, N. J. Kim, and S. K. Kim,
“Ultraviolet–Ultraviolet Hole Burning Spectroscopy in a Quadrupole Ion Trap: Dibenzo[18]crown-6 Complexes with Alkali Metal Cations”
Angew. Chem. Intl. Ed. 51, 7297 (2012).
UV-UV with QIT-TOF
G. Féraud, C. Dedonder, C. Jouvet, Y. Inokuchi, T. Haino, R .Sekiya, and T. Ebata
“Development of Ultraviolet−Ultraviolet Hole-Burning Spectroscopy for Cold Gas-Phase Ions”
J. Phys. Chem. Lett., 5, 1236 (2014).
IR-IR with TOF-TOF
B. M. Elliott, R. A. Relph, J .R. Roscioli, J. C. Bopp, G. H. Gardenier, T. L. Guasco, and M. A. Johnson
“Isolating the spectra of cluster ion isomers using Ar-“tag” -mediated IR-IR double resonance within the vibrational manifolds:
Application to NO2 H2O”
J. Chem. Phys. 129, 094303 (2008).
QIT is a Mass Spectrometer
W. Paul, “Electromagnetic traps for charged and neutral particles”
Nobel Lecture, December 8, 1989.
MS/MS with Dipolar Excitation
0.8
S/N = 5
S/N = 40
0.6
0.4
510
512
0.2
514
516
m/z
518
520
510
512
514
516
m/z
518
520
0.0
0
50000
100000
150000
200000
250000
b7
Frequency (Hz)
10
HPFHLLVY
1
Normalized Intensity
RF Amplitude (V)
1.0
0
0.2
0.4
0.6
0.8
1
1.2
0.1
0.01
Ren
Ren_b7
0.001
Ren_y6
b6
Ren_b6
Ren_y7
0.0001
TNW amplitude (V)
* Tailored Noise Waveform
b7 -H2O
y7
a7
400
b4
b4 -H2O
M -H2O
500
y7
y5 –(H2O)2
b5 y5
b5 -H2O
600
b6 -H2O
700
b7 –(H2O)2 -NH3
b7
b7 -H2O
800
m/z
H. Kang, L. Paša-Tolić, and R. D. Smith, "Targeted Tandem Mass Spectrometry for High-Throughput Comparative Proteomics
Employing NanoLC-FTICR MS with External Ion Dissociation", J. Am. Soc. Mass Spectrom. 18, 1332 (2007).
900
QIT MS with Dipolar Excitation
LTQ XL™ Linear Ion Trap Mass Spectrometer
by Thermo Scientific
http://www.thermoscientific.com/en/product/ltq-xl-linear-ion-trap-mass-spectrometer.html
Fragment Ejection by Tickle RF
400 pF
Auxiliary
Dipolar RF
(tickle)
M+
F+
Probe
F+
Burn
Paul trap
Main RF
fragmentation
50 Ω
1 MΩ
Exit bias
Entrance bias
R. E. March, “An Introduction to Quadrupole Ion Trap Mass Spectrometry”
J. Mass. Spectrom. 32, 351 (1997).
H. Kang, G. Féraud, C. Dedonder-Lardeux, and C. Jouvet, "New Method for Double-Resonance Spectroscopy in a Cold Quadrupole Ion Trap
and Its Application to UV-UV Hole-Burning Spectroscopy of Protonated Adenine Dimer", J. Phys. Chem. Lett. 5, 2760 (2014).
Ejection Profile of AdeH+ (m/z = 136)
fRF = 48.5 kHZ
12
0
10
Ion Signal (mV)
Ion signal (a.u.)
8
6
4
0.1 V
0.2 V
0.3 V
0.4 V
0.5 V
0.6 V
0.7 V
-1
-2
2
0
0.0
0.2
0.4
0.6
RF voltage (V)
0.8
1.0
-3
25.4
25.5
25.6
25.7
TOF (s)
H. Kang, G. Féraud, C. Dedonder-Lardeux, and C. Jouvet, "New Method for Double-Resonance Spectroscopy in a Cold Quadrupole Ion Trap
and Its Application to UV-UV Hole-Burning Spectroscopy of Protonated Adenine Dimer", J. Phys. Chem. Lett. 5, 2760 (2014).
Ejection Profile of AdeH+ (m/z = 136)
- continued
14
VRF = 0.7 V
12
Ion Signal (a.u.)
10
8
m/Δm ~ 20
6
4
2
0
42
44
46
48
50
52
54
RF frequency (kHz)
0.0
48.5 kHz
48.0 kHz
47.5 kHz
47.0 kHz
46.5 kHz
-0.5
Ion Signal (mV)
Ion Signal (mV)
0.0
-1.0
-1.0
f increase
f increase
-1.5
-1.5
25.4
49.0 kHz
49.5 kHz
50.0 kHz
50.5 kHz
51.0 kHz
51.5 kHz
52.0 kHz
-0.5
25.5
25.6
TOF (s)
25.7
25.4
25.5
25.6
25.7
TOF (s)
H. Kang, G. Féraud, C. Dedonder-Lardeux, and C. Jouvet, "New Method for Double-Resonance Spectroscopy in a Cold Quadrupole Ion Trap
and Its Application to UV-UV Hole-Burning Spectroscopy of Protonated Adenine Dimer", J. Phys. Chem. Lett. 5, 2760 (2014).
UV-UV HB Spectroscopy of Ade2H+
b2
Ion Signal (V)
AdeH+
0
-1
-2
-3
-4
0
-1
-2
-3
-4
0
-1
-2
-3
-4
0
-1
-2
-3
-4
0
-1
-2
-3
-4
(a) no laser, no RF
Ade2H+
(a)
a1
34000
35000
b1
a2
36000
37000
38000
(b) burn only
b2
(b)
a2
(c) burn + RF
b1
a1
(c)
-1
a1: 35336 cm
(d) probe + RF
-1
a2: 36164 cm
-1
b1: 35904 cm
(e) burn + probe + RF
-1
b2: 36214 cm
25.0 25.2 25.4 25.6 25.8 26.0 35.4 35.6 35.8 36.0 36.2 36.4
Time of Flight (s)
35000
35500
36000
UV wavenumber / cm
36500
-1
H. Kang, G. Féraud, C. Dedonder-Lardeux, and C. Jouvet, "New Method for Double-Resonance Spectroscopy in a Cold Quadrupole Ion Trap
and Its Application to UV-UV Hole-Burning Spectroscopy of Protonated Adenine Dimer", J. Phys. Chem. Lett. 5, 2760 (2014).
UV-UV HB Spectroscopy of Ade2H+
- continued
b2
(a)
tautomer
Ground
state
energy*
(kJ/mol)
0
1.29
2.85
Excited
state
energy**
(eV)
S1
5.05
S2
5.17
S3
5.27
S4
5.27
S1
S2
S3
S4
4.87
5.04
5.13
5.30
S1
S2
S3
S4
4.86
5.04
5.30
5.39
a1
34000
35000
b1
a2
36000
37000
38000
b2
(b)
a2
b1
a1
(c)
-1
a1: 35336 cm
-1
a2: 36164 cm
-1
b1: 35904 cm
-1
b2: 36214 cm
*MP2/cc-pVDZ
**ADC(2)/cc-pVDZ
35000
35500
36000
UV wavenumber / cm
36500
-1
H. Kang, G. Féraud, C. Dedonder-Lardeux, and C. Jouvet, "New Method for Double-Resonance Spectroscopy in a Cold Quadrupole Ion Trap
and Its Application to UV-UV Hole-Burning Spectroscopy of Protonated Adenine Dimer", J. Phys. Chem. Lett. 5, 2760 (2014).
Summary
• Double resonance spectroscopy in a cold QIT
– Active mass selection in the QIT
– Minimal modification
– Room for improvement in mass resolution
• UV-UV hole-burning spectroscopy of Ade2H+
– Two isomers
– Two excited states with different bandwidth
– Different excited state dynamics?
Acknowledgements
• Christophe Jouvet
• Claude Dedonder
• Géraldine Feraud
Thank you for your attention.