maldi-tof:
TRANSCRIPT
MALDI-TOF:
http://www.raust.is/2003/1/13/raust2003-1-13.pdf
http://biopedia.org/index.php/MALDI-TOF-MS
MALDI-TOF:
n = 1
n = 2
n = 3
::
E
n = 1
n = 2
n = 3
::
E
A A - B
A(n=1) + B
A(n=2) + B
A(n=3) + B
A(n=1)
A(n=2)
A(n=3)
rAB
out
Voltagedevider
HV-2Kv
HX nozzle
TurboPump
TOF
lense
MCP detector
oscilloscope
computer
Excimer Laser
In
út
Dye- Laser
SHG
Time delay200-1200 mS
laser control
Pellin Broca prism
SHG control
In
REMPI-TOF
-1 4
-1 2
-1 0
-8
-6
-4
-2
0
x10
3
3 02 52 01 51 050
Ion m a ss (a m u )
H+
CH+
CH2+
C+ C2+
C2H+
C2H2+
Mag
n jó
na
Ionyield
LASER radiation of C2H2
Mw Time of flight
-1 4
-1 2
-1 0
-8
-6
-4
-2
0
x10
3
3 02 52 01 51 050
Io n m as s (a m u )
H+
CH+
CH2+
C+C2
+
C2H+
C2H2+
Mag
n jó
na
Ionyield
LASER radiation of C2H2
Mw Time of flight
REMPI = Resonance Enhanced MultiPhoton Ionization
Resonance excitation to high energy states of neutral species,followed by photon ionization;For example:
1xhn
2xhn
3xhn
AB
AB+ + e
AB**
2
nxhn
E
-28.5
-28.0
-27.5
-27.0
-26.5
-26.0
x103
4003002001000
Intensity
Mw1 3512
H+
35Cl+
H35Cl+
H37Cl+
12C+
Two photon resonance excitation=82842.36 cm-1
Mass spectrum RCl = HCl
80
70
60
50
40
30
x10
3
8006004002000
82849.4 cm-1
j´=2
82848.76j´=3
82847.8j´=4
82846.44j´=5
82844.84j´=6
82836.36j´=9
82842.36j´=7
82839.8j´=8
82833.6cm-1
82842.88
Mw / rel.
Twophotonexcitation /cm-1
40
30
20
10
0
x10
3
82.85082.84582.84082.835x10
3
Ionyield
REMPI-spectrum
H+
35Cl+
H35Cl+
H37Cl+
cm-1
80
70
60
50
40
30x1
03
8006004002000
82849.4 cm-1
j´=2
82848.76j´=3
82847.8j´=4
82846.44j´=5
82844.84j´=6
82836.36j´=9
82842.36j´=7
82839.8j´=8
82833.6cm-1
82842.88
Mw / rel.
35Cl+
H35Cl+
H37Cl+
30,0323
32,1132
34,2637
36,484
38,7739
41,1336
43,5629
46,0619
82
83
3,6
82
83
5,6
7
82
83
8,4
24
82
84
0,7
14
29
82
84
2,3
6
82
84
4,1
27
27
82
84
6,2
4
82
84
7,9
92
82
84
9,8
26
67
82
85
1,7
46
67-30000-28500-27000-25500-24000-22500-21000-19500-18000-16500-15000-13500-12000-10500-9000-7500-6000-4500-3000-15000
150030004500600075009000
10500120001350015000
2xhv
Mw
35Cl+
37Cl+
H37Cl+
H35Cl+
/cm-1
82833,6
82838,768
82842,88
82846,82857
82850,68
0,7
23
62
4
1
1,3
20
98
33
,10
81
34
,84
9
36
,63
45
38
,46
46
40
,33
93
-29967-28540-27113-25686-24259-22832-21405-19978-18551-17124-15697-14270-12843-11416-9989-8562-7135-5708-4281-2854-14270142728544281570871358562998911416128431427015697
2xhv
Mw /amu
35Cl+
37Cl+
H37Cl+
H35Cl+
H+
/cm-1
82833,6
82835,21
82837,048
82839,456
82840,89714
82842,17714
82843,59273
82845,24
82846,63429
82847,992
82849,4
82850,89333
82852,38667
0,7
23
62
4
0,8
79
42
3
1,0
50
4
1,2
36
55
31
,97
23
32
,96
5
33
,97
3
34
,99
61
36
,03
44
37
,08
78
38
,15
65
39
,24
03
40
,33
93-29715-28300-26885-25470-24055-22640-21225-19810-18395-16980-15565-14150-12735-11320-9905-8490-7075-5660-4245-2830-14150141528304245566070758490990511320127351415015565
2xhv/cm-1
Mw/amu
35Cl+
37Cl+
H37Cl+H35Cl+
H+
REMPI = Resonance Enhanced MultiPhoton Ionization
1xhn
2xhn
2
E
AB
AB+ + e
AB**
A + B+ + e
AB # #
AB+ + e
A+ + B + e
A + B+ + e
A + B/B*
REMPI = Resonance Enhanced MultiPhoton Ionization
1xhn
2xhn
2
E
AB
AB+ + e
AB**
A + B+ + e
AB # #
AB+ + e
A+ + B + eA + B+ + e
A+ + e
B+ + e
MCPdetector
Based on http://en.wikipedia.org/wiki/Photofragment-ion_imaging
=MCP(Micro Channel Plates
= Charge-Couple Device camera
Based on http://pubs.rsc.org/en/content/articlelanding/2010/cp/c001233e#!divAbstract
http://pubs.rsc.org/en/content/articlelanding/2012/cp/c2cp40822h#!divAbstract
=MCP(Micro Channel Plates
= Charge-Couple Device camera
http://pubs.rsc.org/en/content/articlelanding/2010/cp/c001233e#!divAbstract
http://pubs.rsc.org/en/content/articlelanding/2012/cp/c2cp40822h#!divAbstract
r(I-Br)
I + Br
I + Br*
Dt
I++e + Br*I++ e + Br
Based on http://www.chem.queensu.ca/people/faculty/Stolow/Research/QCVibrational.html
Energy
https://www.physics.umn.edu/research/workshops/fluorescence/Fluoro4.pdf
https://www.physics.umn.edu/research/workshops/fluorescence/Fluoro4.pdf
Based on: http://msr.dom.wustl.edu/reflectrons-ion-mirrors/
Without reflectron:
With reflectron:
Detector
tTOF
tTOF
1975-1990:Experiments by use of molecular beams/
Detector
Collision
Molecular beam
Detection
-Collision complexes determined from scattering patterns
John C. PolanyiNobel prize 1986: Dudley Herzbach
Yuan Lee
Molec.beam
LASER beam /LASER geisli:
Sample /Sýni;sameindir
6
LASER LASER-beam/geisli
• Monochromatic light / Einlitt ljós (ein bylgjulengd)• Anisotropic / mjög stefnuháð• High photon concentration /
Mikið magn jafnorkuríkra ljóseinda• Pulsed or continuus /
örstuttir blossar eða samfelld geislun-
The chemical laser /Efna-Laserinn
F + H2 HF* (v´ > 0) + H
http://perg.phys.ksu.edu/vqm/laserweb/ch-6/f6s1t9p4.htm
http://www.raust.is/2003/1/13/raust2003-1-13.pdf
http://www.magnet.fsu.edu/education/tutorials/tools/ionization_esi.html
http://www.rsc.org/chemistryworld/Issues/2003/February/together.asp
http://www.rsc.org/chemistryworld/Issues/2003/February/together.asphttp://www.rsc.org/chemistryworld/Issues/2003/February/
together.asp