On-Line Mass Spectrometric Methods for the Determination of the Primary Products of Fast Pyrolysis of Carbohydrates and for Their Gas-Phase Manipulation

• Published in: Analytical chemistry (Washington) 2013-11, Vol.85 (22), p.10927-10934
• Main Authors: Hurt, Matthew R, Degenstein, John C, Gawecki, Piotr, Borton II, David J, Vinueza, Nelson R, Yang, Linan, Agrawal, Rakesh, Delgass, W. Nicholas, Ribeiro, Fabio H, Kenttämaa, Hilkka I
• Format: Article
• Language: English
• Subjects: Ammonium hydroxide; Analytical chemistry; Atmospheric pressure; Carbohydrates; Chemical compounds; Chloroform; Fragmentation; Ionization; Mass spectrometry; Pyrolysis; Quenching (cooling); Spectroscopy
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac402380h

Mass spectrometric methodology was developed for the determination and manipulation of the primary products of fast pyrolysis of carbohydrates. To determine the true primary pyrolysis products, a very fast heating pyroprobe was coupled to a linear quadrupole ion trap mass spectrometer through a custom-built adaptor. A home-built flow tube that simulates pyrolysis reactor conditions was used to examine the secondary reactions of the primary products. Depending on the experiment, the pyrolysis products were either evaporated and quenched or allowed to react for a period of time. The quenched products were ionized in an atmospheric pressure chemical ionization (APCI) source infused with one of two ionization reagents, chloroform or ammonium hydroxide, to aid in ionization. During APCI in negative ion mode, chloroform produces chloride anions that are known to readily add to carbohydrates with little bias and little to no fragmentation. On the other hand, in positive ion mode APCI, ammonium hydroxide forms ammonium adducts with carbohydrates with little to no fragmentation. The latter method ionizes compounds that are not readily ionized upon negative ion mode APCI, such as furan derivatives. Six model compounds were studied to verify the ability of the ionization methods to ionize known pyrolysis products: glycolaldehyde, hydroxyacetone, furfural, 5-hydroxymethylfurfural, levoglucosan, and cellobiosan. The method was then used to examine fast pyrolysis of cellobiose. The primary fast pyrolysis products were determined to consist of only a handful of compounds that quickly polymerize to form anhydro-oligosaccharides when allowed to react at high temperatures for an extended period of time.