Collisional Dynamics Simulations Revealing Fragmentation Properties of Zn(II)-Bound Poly-Peptide

<div> <div> <div> <p>Chemical dynamics simulations are performed to study the collision induced gas phase unimolecular fragmentation of a model peptide with the sequence acetyl-His1-Cys2-Gly3-Pro4-Tyr5-His6-Cys7 (analogue methanobactin peptide-5, amb5) and in particular to explore the role of zinc binding on reactivity. Fragmentation pathways, their mechanisms, and collision energy transfer are discussed. The probability distributions of the pathways are compared with the results of the experimental IM-MS, MS/MS spectrum and previous thermal simulations. Collisional activation gives both statistical and non-statistical fragmentation pathways with non-statistical shattering mechanisms accounting for a relevant percentage of reactive trajectories, becoming dominant at higher energies. The tetra-coordination of zinc changes qualitative and quantitative fragmentation, in particular the shattering. The collision energy threshold for the shattering mechanism was found to be 118.9 kcal/mol which is substantially higher than the statistical Arrhenius activation barrier of 35.8 kcal/mol identified previously during thermal simulations. This difference can be attributed to the tetra-coordinated zinc complex that hinders the availability of the sidechains to undergo direct collision with the Ar projectile. </p> </div> </div> </div>

Collisional Dynamics Simulations Revealing Fragmentation Properties of Zn(II)-Bound Poly-Peptide

<div> <div> <div> <p>Chemical dynamics simulations are performed to study the collision induced gas phase unimolecular fragmentation of a model peptide with the sequence acetyl-His1-Cys2-Gly3-Pro4-Tyr5-His6-Cys7 (analogue methanobactin peptide-5, amb5) and in particular to explore the role of zinc binding on reactivity. Fragmentation pathways, their mechanisms, and collision energy transfer are discussed. The probability distributions of the pathways are compared with the results of the experimental IM-MS, MS/MS spectrum and previous thermal simulations. Collisional activation gives both statistical and non-statistical fragmentation pathways with non-statistical shattering mechanisms accounting for a relevant percentage of reactive trajectories, becoming dominant at higher energies. The tetra-coordination of zinc changes qualitative and quantitative fragmentation, in particular the shattering. The collision energy threshold for the shattering mechanism was found to be 118.9 kcal/mol which is substantially higher than the statistical Arrhenius activation barrier of 35.8 kcal/mol identified previously during thermal simulations. This difference can be attributed to the tetra-coordinated zinc complex that hinders the availability of the sidechains to undergo direct collision with the Ar projectile. </p> </div> </div> </div>

Emission Characteristics of Copper Ionic Lines from the 3d95s-3d94p Transition in a Low-Pressure Laser-Induced Plasma

The Emission Characteristic of Copper Ionic Lines Requiring Large Excitation Energies Was Investigated in Low-Pressure Laser-Induced Plasma Spectroscopy (LP-LIPS), when Argon Was Employed as Plasma Gas. The Excited Mechanism of the Ironic Lines Whose Electron Transitions Were Assigned to the 3d95s-3d94p Configuration Was Understood from the Time-Resolved Spectra of Copper. The Emission Intensity of the Copper Emission Lines, Measured in a Time-Resolved Mode, Was Extremely Dependent on the Kind of Copper Lines and the Upper Energy. Generally, their Emission Intensities Dramatically Decreased with the Duration Time, along with the Recombination as Well as the De-Excitation of Copper Ions Requiring Larger Kinetics Energy which Mainly Were Produced in a Hot Breakdown Plasma. The Emission Behavior Excited from the 3d95s-3d94p Transition, such as the Cu II 254.4 nm and the Cu II 276.9 nm Lines, Was Generally Similar to that from 3d94p-3d94s Transition, although their Excitation Energies Were Different. This Effect Would Result from a Common and Dominant Ionization /excitation Mechanism, which Was Collision Energy Transfer from Energetic Particles such as Fast Electrons.