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
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 – PEPICOInfrared – IRMPD, tagging, BIRDUV-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
Energy (eV, CM)
0.0 2.0 4.0 6.0
Cro
ss S
ectio
n (Å
2 )
10-3
10-2
10-1
100
101
Energy (eV Lab)
0.0 5.0 10.0 15.0
Rb+(12C4) + Xe
Rb+ + 12C4 + Xe
ESI
DC-FT/10
Structural and Energetic Information
Means of generating ions changes structure
More, Ray, Armentrout, J. Phys. Chem. A 1997, 101, 7007.
Armentrout, Austin, Rodgers, Int. J. Mass Spectrom. 2012, 330-332, 16.
Thermodynamic
Kinetic trapping
Structural and Energetic Information
Chen, Rodgers, J. Am. Chem. Soc. 2012, 134, 5863
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
Donald, Williams, Pure Appl. Chem. 2011, 83, 2129
Electron capture dissociation of M3+
(NH3)6(H2O)55
Also UV photodissociation of M2+
(H2O)n
Energetic Information - Electrochemistry
Relative solution phase
Absolute gas phase
Energetic Information – Biochemistry
TCID 0 K Threshold Energies (kJ/mol)
80 100 120 140 160
The
oret
ical
0 K
AE
s/E
ntha
lpie
s (k
J/m
ol)
80
100
120
140
160
[Cyd+H]+
[Urd+H]+
[Thd+H]+
[Guo+H]+
[Ado+H]+
[dAdo+H]+
[dCyd+H]+
[dGuo+H]+
[dThy+H]+
[dUrd+H]+
DNA 4.1 ± 4.3 RNA 6.5 ± 8.6
MAD ± SDEnergy required for
glycosidic bond cleavage: DNA < RNA
Glycosidic bond cleavage of nucleosides and deoxynucleosides
Protonated deoxyadenosine [Ado+H+] N3, syn, C2'-endo
Wu and Rodgers, work in progress
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