Energetics and Dynamics of Dissociation of Deprotonated Peptides: Fragmentation of Angiotensin Analogs

Journal Article · Thu Dec 01 04:00:00 EST 2011 · International Journal of Mass Spectrometry

DOI:https://doi.org/10.1016/j.ijms.2011.07.003· OSTI ID:1035739

Laskin, Julia; Yang, Zhibo

We present a first study of the energetics and dynamics of dissociation of deprotonated peptides using time- and collision-energy resolved surface-induced dissociation (SID) experiments. SID of four model peptides: RVYIHPF, HVYIHPF, DRVYIHPF, and DHVYIHPF was studied using a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) configured for studying ion-surface collisions. Energy and entropy effects for the overall decomposition of the precursor ion were deduced by modeling the time- and collision energy-resolved survival curves using an RRKM based approach developed in our laboratory. The results were compared to the energetics and dynamics of dissociation of the corresponding protonated species. We demonstrate that acidic peptides are less stable in the negative mode because of the low threshold associated with the kinetically hindered loss of H2O from [M-H]- ions. Comparison between the two basic peptides indicates that the lower stability of the [M-H]- ion of RVYIHPF as compared to HVYIHPF towards fragmentation is attributed to the differences in fragmentation mechanisms. Specifically, threshold energy associated with losses of NH3 and NHCNH from RVYIHPF is lower than the barrier for backbone fragmentation that dominates gas-phase decomposition of HVYIHPF. The results provide a first quantitative comparison between the energetics and dynamics of dissociation of [M+H]+ and [M-H]- ions of acidic and basic peptides.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1035739
• Report Number(s): PNNL-SA-80305; KC0302020
• Journal Information: International Journal of Mass Spectrometry, Journal Name: International Journal of Mass Spectrometry Journal Issue: 2-3 Vol. 308
• Country of Publication: United States
• Language: English

Related Subjects

59 BASIC BIOLOGICAL SCIENCES
60 APPLIED LIFE SCIENCES
ANGIOTENSIN
DISSOCIATION
ENTROPY
FRAGMENTATION
ION CYCLOTRON-RESONANCE
MASS SPECTROMETERS
PEPTIDES
PRECURSOR
SIMULATION
STABILITY
SURVIVAL CURVES
THRESHOLD ENERGY