MALDI-TOF:

http://www.raust.is/2003/1/13/raust2003-1-13.pdf

http://biopedia.org/index.php/MALDI-TOF-MS

MALDI-TOF:

E

n = 1

n = 2

n = 3

:n = 4

l = 0/s l = 1/p l = 2/d l = 3/f

::

::

::

.

A > H.

t.d. C(6e-)

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

1xhn

2

E

AB

AB+ + e

AB**

REMPI = Resonance Enhanced MultiPhoton Ionization

1xhn

2xhn

2

E

AB

AB+ + e

AB**

(2 + 1) REMPI

REMPI = Resonance Enhanced MultiPhoton Ionization

1xhn

2xhn

2

E

AB

AB+ + e

AB**

A + B+ + e

REMPI = Resonance Enhanced MultiPhoton Ionization

1xhn

2xhn

3xhn

AB

AB+ + e

AB**

2

nxhn

E

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

Orka

HCCH:

HCCH*:

Orka

C2 H2

HCCH*:

C2

+

+

Orka

HCCH*:

Orka

HCCH*:

CH2C

-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

C2H2

BigOrganic molecules : Life(?)

Interstellar space

???

C2H2

Big Organic molecules : Life(?)

Interstellarspace

???C2

CCH2

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+

85.36x103

85.3585.3485.3385.32cm

-1

H37

Cl+

H+

37Cl

+

35Cl

+

H35

Cl+

REMPI = Resonance Enhanced MultiPhoton Ionization

1xhn

2xhn

2

E

AB

AB+ + e

AB**

A + B+ + e

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

Unsymmetric images!?

DtLaser beams:Polarized light

https://www.physics.umn.edu/research/workshops/fluorescence/Fluoro4.pdf

https://www.physics.umn.edu/research/workshops/fluorescence/Fluoro4.pdf

Accellerationregion

FlightRegion

Reflectron MS

Magnetic Reflector

Based on: http://msr.dom.wustl.edu/reflectrons-ion-mirrors/

Without reflectron:

With reflectron:

Detector

tTOF

tTOF

Nozzle

2) Velocity selctionby jet cooling /2) Hraðavalframkvæmt með“gasúðara”

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

Light /Ljós ?

White light/Hvítt ljós

GulurRauður

GrænnBlár

Prism /Gler-strendingur

l /Bylgju-lengd

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-

Laser activity /Laser virkni:

He/Ne & Dye laser /Lit-LASER

CO2 and Excimer LASERs

The chemical laser /Efna-Laserinn

F + H2 HF* (v´ > 0) + H

http://perg.phys.ksu.edu/vqm/laserweb/ch-6/f6s1t9p4.htm

The chemical laser /Efna-Laserinn

Efna-LASER

HOMO

LUMO

R(A-B)

E

E

R(A-B)

E

R(A-B)

E

R(A-B)

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