The synthesis of 1-butyl-2,3-dimethyl-4-vinylimidazolium triflate, its polymerization, and ion exchange to yield a trio of 1-butyl-2,3-dimethyl-4-vinylimidazolium polymers is described. Irrespective of the nature of the anion, substitution at the 2-position of the imidazolium moiety substantially increases the distance between the anion and cation. The methyl substituent at the 2-position also served to expose the importance of H-bonding for the attractive potential between imidazolium moiety and anions in polymers without a methyl group at the 2-position. The thermal characteristics of poly(1-butyl-2,3-dimethyl-4-vinylimidazolium) salts and corresponding poly(1-ethyl-3-methyl-4-vinylimidazolium) salts were evaluated. While the mid-point glass transition temperatures, Tg-mid, for 1-ethyl-3-methyl-4-vinylimidazolium polymers with CF3SO3−, (CF3SO2)2N− and PF6− counterions, were 153 °C, 88 °C and 200 °C, respectively, the Tg-mid values for 1-butyl-2,3-dimethyl-4vinylimidazolium polymers with corresponding counter-ions were tightly clustered at 98 °C, 99 °C and 84 °C, respectively. This dramatically reduced influence of the anion type on the glass transition temperature was attributed to the increased distance between the center of the anions and cations in the 1-butyl-2,3-dimethyl-4-vinylimidazolium polymer set, and minimal H-bonding interactions between the respective anions and the 1-butyl-2,3-dimethyl-4-vinylimidazolium moiety. It is believed that this is the first observation of substantial independence of the glass transition of an ionic polymer on the nature of its counterion.
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Nitro Indole Derivatives as Novel Dual-Polarity Matrices for MALDIMass Spectrometry and Imaging with Broad Applications
A new matrix framework is presented in this studyfor the improved ionization efficiency of complex mixtures by matrix-assisted laser desorption ionization (MALDI) mass spectrometry/imaging. Five nitro indole (NI) derivatives [3-methyl-4-nitro-1H-indole (3,4-MNI), 3-methyl-6-nitro-1H-indole(3,6-MNI), 2,3-dimethyl-4-nitro-1H-indole (2,3,4-DMNI), 2,3-dimethyl-6-nitro-1H-indole (2,3,6-DMNI), and 4-nitro-1H-indole(4-NI)] were synthesized and shown to produce both positive and negative ions with a broad class of analytes as MALDI matrices. NI matrices were compared to several common matrices, such as 2,5-dihydroxybenzoic acid (DHB), alpha-cyano-4-hydroxylcinnamicacid (CHCA), sinapinic acid (SA), 1,5-diaminonaphthelene (1,5-DAN), and 9-aminoacridine (9-AA), for the analysis of lipid, peptide, protein, glycan, and perfluorooctanesulfonic acid (PFOS) compounds. 3,4-MNI demonstrated the best performance among the NI matrices. This matrix resulted in reduced ion suppression and better detection sensitivity for complex mixtures, for example, egg lipids/milk proteins/PFOS in tap water, while 2,3,6-DMNI was the best matrix for blueberry tissue imaging. Several important aspects of this work are reported: (1) dual-polarity ion production with NI matrices and complex mixtures; (2) quantitative analysis of PFOS with a LOQ of 0.5 ppb in tap water and 0.05 ppb in MQ water (without solid phase extraction enrichment), with accuracy and precision within 5%; (3) MALDI imaging with 2,3,6-DMNI as a matrix for plant metabolite/lipid identification with ionization enhancement in the negative ion mode m/z 600−900 region; and (4) development of a thin film deposition under/above tissue method for MALDI imaging with a vacuum sublimation matrix on a high-vacuum MALDI instrument.
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- Award ID(s):
- 2045005
- PAR ID:
- 10586338
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Analytical Chemistry
- Volume:
- 96
- Issue:
- 4
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 1668–1677
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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