Assessing the Indirect Photochemical

Transformation of Dissolved Combined

Amino Acids through the Use of
Systematically Designed Histidine-
Containing Oligopeptides
DOI: 10.1021/acs.est.5b03498

 Chiheng Chu
 Rachel A. Lundeen
 Michael Sander
 Kristopher McNeill *

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Cite this: Environ. Sci. Technol. 2015, 49, 21, 12798-12807
Publication Date:October 1, 2015
https://doi.org/10.1021/acs.est.5b03498
Copyright © 2015 American Chemical Society
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Supporting Info (1)» Supporting Information

SUBJECTS:
 Sorption

 Environmental Science & Technology

Abstract

Photooxidation is an important abiotic transformation pathway for amino acids (AAs) in

sunlit waters. Although dissolved free AAs are well studied, the photooxidation of
dissolved combined AAs (DCAAs) remains poorly investigated. This study is a
systematic investigation of the effect of neighboring photostable AA residues (i.e.,
aliphatic, cationic, anionic, or aromatic residues) on the environmental indirect
photochemical transformation of histidine (His) in His-containing oligopeptides. The
pKa values of His residues in the studied oligopeptides were found to be between 4.3 and
8.1. Accordingly, the phototransformation rate constants of the His-containing
oligopeptides were highly pH-dependent in an environmentally relevant pH range with
higher reactivity for neutral His than for the protonated species. The photostable AA
residues significantly modulated the photoreactivity of oligopeptides either through
altering the accessibility of His to photochemically produced oxidants or through
shifting the pKa values of His residues. In addition, the influence of neighboring
photostable AA residues on the sorption-enhanced phototransformation of
oligopeptides in solutions containing chromophoric dissolved organic matter (CDOM)
was assessed. The constituent photostable AA residues promoted sorption of His-
containing oligopeptides to CDOM macromolecules through electrostatic attraction,
hydrophobic effects, and/or low-barrier hydrogen bonds, and subsequently increased
the apparent phototransformation rate constants by up to 2 orders of magnitude.