Oligo p-Phenylenevinylene Derivatives as Electron Transfer Matrices for UV-MALDI

• Published in: Journal of the American Society for Mass Spectrometry 2017-12, Vol.28 (12), p.2548-2560
• Main Authors: Castellanos-García, Laura J., Agudelo, Brian Castro, Rosales, Hernando F., Cely, Melissa, Ochoa-Puentes, Christian, Blanco-Tirado, Cristian, Sierra, Cesar A., Combariza, Marianny Y.
• Format: Article
• Language: English
• Subjects: ABSORPTION; Absorption spectra; Absorptivity; Adducts; Analytical Chemistry; Bioinformatics; Biotechnology; Chemistry; Chemistry and Materials Science; COMPARATIVE EVALUATIONS; Derivatives; ELECTRON TRANSFER; ELECTRONS; INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; IONIZATION POTENTIAL; Ionization potentials; Ions; Mass spectrometry; Oligomers; Optical properties; Organic Chemistry; PORPHYRINS; Proteomics; Research Article; SYNTHESIS; THRESHOLD ENERGY; Transfer matrices
• ISSN: 1044-0305; 1879-1123
• DOI: 10.1007/s13361-017-1783-z

Phenylenevinylene oligomers (PVs) have outstanding photophysical characteristics for applications in the growing field of organic electronics. Yet, PVs are also versatile molecules, the optical and physicochemical properties of which can be tuned by manipulation of their structure. We report the synthesis, photophysical, and MS characterization of eight PV derivatives with potential value as electron transfer (ET) matrices for UV-MALDI. UV-vis analysis show the presence of strong characteristic absorption bands in the UV region and molar absorptivities at 355 nm similar or higher than those of traditional proton (CHCA) and ET (DCTB) MALDI matrices. Most of the PVs exhibit non-radiative quantum yields (φ) above 0.5, indicating favorable thermal decay. Ionization potential values (IP) for PVs, calculated by the Electron Propagator Theory (EPT), range from 6.88 to 7.96 eV, making these oligomers good candidates as matrices for ET ionization. LDI analysis of PVs shows only the presence of radical cations (M +. ) in positive ion mode and absence of clusters, adducts, or protonated species; in addition, M +. threshold energies for PVs are lower than for DCTB. We also tested the performance of four selected PVs as ET MALDI matrices for analytes ranging from porphyrins and phthalocyanines to polyaromatic compounds. Two of the four PVs show S/N enhancement of 1961% to 304% in comparison to LDI, and laser energy thresholds from 0.17 μJ to 0.47 μJ compared to 0.58 μJ for DCTB. The use of PV matrices also results in lower LODs (low fmol range) whereas LDI LODs range from pmol to nmol. Graphical Abstract ᅟ