Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

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1 Supplementary Material for Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides Christopher L. Moss, a Thomas W. Chung, a Jean A. Wyer, b Steen Brøndsted Nielsen, b Preben Hvelplund, b František Tureček a * a Department of Chemistry, Bagley Hall, Box 35170, University of Washington, Seattle, WA , USA b Department of Physics and Astronomy, University of Aarhus, Aarhus, Denmark Manuscript submitted to the Journal of the American Society for Mass Spectrometry, October Figure S1. Relative intensities of z 1 -z 5 ions in the ETD spectra of pentapeptide ions. 1

2 Relative Intensity (%) Relative Intensity (%) a b c -H 3 PO 4 z 3 (397) -H 3 PO 4 m/z z 4 (468) m/z Relative Intensity (%) z 2 (326) Figure S2. ETD-CID-MS 3 mass spectra of (a) z 4, (b) z 3, and (c) z 2 ions from (AAApSR + 2H) 2+ (4a 2+ ). m/z 2

3 12 10 a 457 -H 3 PO 4 Relative intensity (%) y 2 y 3 y psaaar (555) m/z 12 b 457 -H 3 PO 4 Relative intensity (%) y 2 y AApSAR (555) m/z 12 c 457 -H 3 PO 4 Relative intensity (%) AAApSR (555) m/z Figure S3. ETD-CID-MS 3 mass spectra of m/z 555 ions from (a) 1a 2+, (b) 3a 2+, and (c) 4a 2+ showing a predominant loss of phosphoric acid at m/z

4 D E 0.26 C B A X 0.00 ev Figure S4. Electronic states in (AAApSR + 2H) + after vertical eletron attachement. Excitation energies are from TD-DFT calculations with B3LYP/ G(2d,p). 4

5 Dipolar Field Effects μ = 10 D Å MO12,13, 3p x, 3p y 1.56 ev MO11,12, 3p x, 3p y 1.45 ev MO13, 3p z 1.41 ev 1.48 ev MO11, 3p z MO10, SOMO, 3s MO10, SOMO Figure S5. Frontier orbitals in CH 3 NH 3 radicals. Left panel: 3s and 3p orbitals without a dipolar field. Right panel: 3s and 3p orbitals in the presence of a superimposed 10-D dipole oriented along the C N bond. Excitation energies are from TD-DFT calculations with B3LYP/ G(2df,2p) + additional very diffuse functions on N according to ref. [69]. 5

6 Table S1. Force-field Parameters for molecular dynamics calculations of phosphopeptide ions. Partial Charges: Bond Potentials V(bond) = K b (b b 0 ) 2 C β 0.08 Bond K b (kcal/(mol Å 2 ) b 0 (Å) H β 0.09 C β O γ O γ 0.50 Angle Potentials V(angle) = K θ (θ θ 0 ) 2 P 1.9 Angle K θ (kcal/(mol rad 2 ) θ (degrees) O phosphony l 0.82 C α C β O γ O hydroxyl 0.68 C β O γ P H phosphate 0.34 H β C β O γ Dihedral Potential V(dihedral) = K χ [1 + cos(nχ)-δ] K χ (kcal/mol) n δ (degrees) C α C β O γ P C α C β O γ P C α C β O γ P C β O γ P O phosphonyl C β O γ P O hydroxyl C β O γ P O hydroxyl

7 Table S2. B3LYP/6-31+G(d,p) optimized structure of (psaaar + 2H) 2+ ion 1a 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

8 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S3. B3LYP/6-31+G(d,p) optimized structure of (psaaar + 2H) 2+ ion 1b 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

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10 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S4. B3LYP/6-31+G(d,p) optimized structure of (psaaar + 2H) 2+ ion 1c 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

11 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S5. B3LYP/6-31+G(d,p) optimized structure of (psaaar + 2H) 2+ ion 1d 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

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13 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S6. B3LYP/6-31+G(d,p) optimized structure of (psaaar + 2H) 2+ ion 1e 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

14 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S7. B3LYP/6-31+G(d,p) optimized structure of (ApSAAR + 2H) 2+ ion 2a 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

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16 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S8. B3LYP/6-31+G(d,p) optimized structure of (ApSAAR + 2H) 2+ ion 2b 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

17 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S9. B3LYP/6-31+G(d,p) optimized structure of (ApSAAR + 2H) 2+ ion 2c

18 Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

19 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S10. B3LYP/6-31+G(d,p) optimized structure of (ApSAAR + 2H) 2+ ion 2d 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

20 Rotational constants (GHZ):

21 E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S11. B3LYP/6-31+G(d,p) optimized structure of (ApSAAR + 2H) 2+ ion 2e 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

22 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S12. B3LYP/6-31+G(d,p) optimized structure of (AApSAR + 2H) 2+ ion 3a 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

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24 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S13. B3LYP/6-31+G(d,p) optimized structure of (AApSAR + 2H) 2+ ion 3b 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

25 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S14. B3LYP/6-31+G(d,p) optimized structure of (AApSAR + 2H) 2+ ion 3c 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

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27 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S15. B3LYP/6-31+G(d,p) optimized structure of (AApSAR + 2H) 2+ ion 3d 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

28 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S16. B3LYP/6-31+G(d,p) optimized structure of (AApSAR + 2H) 2+ ion 3e 2+. Standard orientation: 28

29 Center Atomic Atomic Coordinates (Angstroms)

30 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S17. B3LYP/6-31+G(d,p) optimized structure of (AAApSR + 2H) 2+ ion 4a 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)

31 Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. E[B3LYP/ G(2d,p)] = a.u. 31

32 E[MP2/ G(2d,p)] = a.u. ZPVE = kj mol -1. Table S18. B3LYP/6-31+G(d,p) optimized structure of (AAApSR + 2H) 2+ ion 4b 2+. Standard orientation: Center Atomic Atomic Coordinates (Angstroms)