Tandem Mass Spectrometric Analysis of Novel Peptide-Modified Gemini Surfactants Used as Gene Delivery Vectors.
Date
2017-05-31
Authors
El-Aneed, Anas
Al-Dulaymi, Mays
Journal Title
Journal ISSN
Volume Title
Publisher
Wiley
ORCID
Type
Degree Level
Abstract
Diquaternary ammonium gemini surfactants have emerged as effective gene delivery vectors. A novel series of 11 peptide-modified compounds was synthesized, showing promising results in delivering genetic materials. The purpose of this work is to elucidate the tandem mass spectrometric (MS/MS) dissociation behavior of these novel molecules establishing a generalized MS/MS fingerprint. Exact mass measurements were achieved using a hybrid quadrupole orthogonal time-of-flight mass spectrometer, and a multi-stage MS/MS analysis was conducted using a triple quadrupole-linear ion trap mass spectrometer. Both instruments were operated in the positive ionization mode and are equipped with electrospray ionization. Abundant triply charged [M+H]3+ species were observed in the single-stage analysis of all the evaluated compounds with mass accuracies of less than 8 ppm in mass error. MS/MS analysis showed that the evaluated gemini surfactants exhibited peptide-related dissociation characteristics because of the presence of amino acids within the compounds' spacer region. In particular, diagnostic product ions were originated from the neutral loss of ammonia from the amino acids' side chain resulting in the formation of pipecolic acid at the N-terminus part of the gemini surfactants. In addition, a charge-directed amide bond cleavage was initiated by the amino acids' side chain producing a protonated α-amino-ε-caprolactam ion and its complimentary C-terminus ion that contains quaternary amines. MS/MS and MS3 analysis revealed common fragmentation behavior among all tested compounds, resulting in the production of a universal MS/MS fragmentation pathway.
Description
Keywords
gemini surfactants; peptide-modified delivery vectors; tandem mass spectrometry; universal MS/MS fragmentation
Citation
Al-Dulaymi, M., and El-Aneed, A. (2017) Tandem mass spectrometric analysis of novel peptide-modified gemini surfactants used as gene delivery vectors. J. Mass Spectrom., 52: 353–366. doi: 10.1002/jms.3933.
Degree
Department
Program
Advisor
Committee
Citation
Al-Dulaymi, M., and El-Aneed, A. (2017) Tandem mass spectrometric analysis of novel peptide-modified gemini surfactants used as gene delivery vectors. J. Mass Spectrom., 52: 353–366. doi: 10.1002/jms.3933.
Part Of
item.page.relation.ispartofseries
DOI
10.1002/jms.3933
item.page.identifier.pmid
28409852