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

Theo

retic

al 0

K A

Es/

Ent

halp

ies

(kJ/

mol

)

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