English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Femtosecond Pumping Rate Dependence of Fragmentation Mechanisms in Matrix-Assisted Laser Desorption Ionization

Pieterse, C. L., Busse, F., Tellkamp, F., Robertson, W., & Miller, R. J. D. (2018). Femtosecond Pumping Rate Dependence of Fragmentation Mechanisms in Matrix-Assisted Laser Desorption Ionization. doi:10.26434/chemrxiv.6450380.v1.

Item is

Basic

show hide
Item Permalink: http://hdl.handle.net/21.11116/0000-0002-1493-1 Version Permalink: http://hdl.handle.net/21.11116/0000-0002-6D55-5
Genre: Paper

Files

show Files
hide Files
:
ACLPaperV6.pdf (Preprint), 2MB
Name:
ACLPaperV6.pdf
Description:
Downloaded from chemrxiv.org: 2018-09-13
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
2018
Copyright Info:
© the Author(s)

Locators

show
hide
Description:
-

Creators

show
hide
 Creators:
Pieterse, C. L.1, Author              
Busse, Frederik1, Author              
Tellkamp, F.2, Author              
Robertson, W.1, Author              
Miller, R. J. D.1, 3, Author              
Affiliations:
1Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
2Machine Physics, Scientific Service Units, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2074322              
3Departments of Chemistry and Physics, University of Toronto, ou_persistent22              

Content

show
hide
Free keywords: Femtosecond, Desorption, Ionization, Fragmentation, Benzyltriphenylphosphonium
 Abstract: The benzyltriphenylphosphonium (BTP) thermometer ion is utilized to characterize the fragmentation mechanisms of matrix-assisted laser desorption/ionization (MALDI) for femtosecond ultraviolet laser pulses. We demonstrate that the survival yield of BTP approaches unity under these conditions, which suggests that a minimal amount of fragmentation is occurring. It is also shown that the survival yield of BTP is insensitive to the laser fluence. However, the magnitude of fragmentation for the matrix increased notably for the same fluence range. These results indicate that the amount of energy transferred from the matrix ions to the BTP thermometer ions is minimal because the femtosecond desorption applied here occur within the stress-confinement regime. This observation is in agreement with recent molecular dynamics simulations which predict that it should be possible to separate both desorption and ionization processes in the regime of stress-confined desorption. Our results indicate that angiotensin is the largest biomolecule which could be routinely measured with these pulses. A mass upper-limit supports the hypothesis that ionization is hindered by the increased thermal gradients imposed in the lattice and associated velocity distribution within the ablation process from the much higher lattice heating rate with femtosecond pulses. This effect results in the temporal overlap between the neutral molecules and the matrix ions being too small to result in sufficient proton exchange for ionization.

Details

show
hide
Language(s): eng - English
 Dates: 2018-06-062018-06-07
 Publication Status: Published online
 Pages: 20
 Publishing info: -
 Table of Contents: -
 Rev. Method: No review
 Identifiers: DOI: 10.26434/chemrxiv.6450380.v1
 Degree: -

Event

show

Legal Case

show

Project information

show

Source

show