Ion Activation and Dissociation
Vicki Wysocki (University of Arizona)
Probing Influence of Charge on Structures of Protein Complexes with Surface
Induced Dissociation and Ion Mobility
Bela Paizs (German Cancer Research Center, Heidelberg)
Efficient Computation of Structures and Reactions of Doubly Protonated
Tryptic Peptides and Their Fragments
Julia Laskin (Pacific Northwest National Laboratory)
Large Metal and Metal-Oxide Clusters in the Gas Phase and on Surfaces
Ryan Julian (University of California, Riverside)
Radical Recombination Labeling: Click Chemistry in the Gas Phase
Oliver Hampe (Karlsruhe Institute of Technology)
Multiply Charged Anions: Infrared Spectroscopy and Photoelectron
Spectroscopy on Adenonsine 5'-Di and Triphosphate Anions
Ion Activation and Dissociation
What are the means of ion activation?
Collisions with gases:
Collision-induced dissociation (CID)
Reactions
Collisions with electrons:
Electron capture dissociation (ECD)
Electron ionization
Collisions with other ions:
Electron transfer dissociation (ETD)
Collisions with surfaces:
Surface induced dissociation (SID)
Collisions with photons:
Photoionization – PEPICO
Infrared
– IRMPD, tagging, BIRD
UV-visible
Ion Activation and Dissociation
What factors are influential?
Structure (conformation) of initial ion
Extent and distribution of energy deposited
Timescale of experiment (lifetimes)
Mechanism of excitation (rovibronic vs electronic)
What do we learn?
Structure
Energetics
Kinetics
Reactivity
Structural and Energetic Information
Energy (eV Lab)
0.0
2
Cross Section (Å )
101
10.0
15.0
Means of
generating
ions changes
structure
DC-FT/10
ESI
100
10-1
10
5.0
-2
More, Ray,
Armentrout, J.
Phys. Chem. A
1997, 101, 7007.
Thermodynamic
Armentrout,
Austin, Rodgers,
Int. J. Mass
Spectrom. 2012,
330-332, 16.
+
Rb (12C4) + Xe
+
Rb + 12C4 + Xe
10
-3
0.0
Kinetic trapping
2.0
4.0
Energy (eV, CM)
6.0
Structural and Energetic Information
Molecular Recognition of Amino Acids by 18-Crown-6
Binding energy
(Gly)H+-18C6
(N-terminus)
>
(Lys)H+-18C6
>
(His)H+-18C6
>
(Arg)H+-18C6
Chen, Rodgers, J. Am. Chem. Soc. 2012, 134, 5863
Energetic Information - Electrochemistry
Electron capture dissociation of
M3+(NH3)6(H2O)55
Also UV photodissociation of
M2+(H2O)n
Absolute
gas phase
Donald, Williams, Pure Appl. Chem. 2011, 83, 2129
Relative
solution phase
Energetic Information – Biochemistry
Protonated deoxyadenosine
[Ado+H+] N3, syn, C2'-endo
Energy required for
glycosidic bond cleavage:
DNA < RNA
Wu and Rodgers, work in progress
Theoretical 0 K AEs/Enthalpies (kJ/mol)
Glycosidic bond cleavage of nucleosides and deoxynucleosides
[Ado+H]+
[dAdo+H]+
160
140
[Guo+H]+
[Urd+H]+
[Thd+H]+
120
[dUrd+H]+
100
[Cyd+H]+
[dGuo+H]+
[dCyd+H]+
80 [dThy+H]+
MAD ± SD
DNA 4.1 ± 4.3
RNA 6.5 ± 8.6
80
100
120
140
160
TCID 0 K Threshold Energies (kJ/mol)
Ion Activation and Dissociation
Vicki Wysocki (University of Arizona)
Probing Influence of Charge on Structures of Protein Complexes with Surface
Induced Dissociation and Ion Mobility
Bela Paizs (German Cancer Research Center, Heidelberg)
Efficient Computation of Structures and Reactions of Doubly Protonated
Tryptic Peptides and Their Fragments
Julia Laskin (Pacific Northwest National Laboratory)
Large Metal and Metal-Oxide Clusters in the Gas Phase and on Surfaces
Ryan Julian (University of California, Riverside)
Radical Recombination Labeling: Click Chemistry in the Gas Phase
Oliver Hampe (Karlsruhe Institute of Technology)
Multiply Charged Anions: Infrared Spectroscopy and Photoelectron
Spectroscopy on Adenonsine 5'-Di and Triphosphate Anions