Identification of alkaline-induced thiolyl-chlorogenic acid conjugates with cysteine and glutathione

Charles T Drucker; Amanda R Cicali; Andrew M P Roberts; Christine A Hughey; Lilian W Senger

doi:10.1016/j.foodchem.2023.136267

Identification of alkaline-induced thiolyl-chlorogenic acid conjugates with cysteine and glutathione

Food Chem. 2023 Oct 15:423:136267. doi: 10.1016/j.foodchem.2023.136267. Epub 2023 Apr 28.

Authors

Charles T Drucker¹, Amanda R Cicali², Andrew M P Roberts³, Christine A Hughey⁴, Lilian W Senger⁵

Affiliations

¹ Food Science Program, Schmid College of Science and Technology, Chapman University, University Drive, Orange, CA 92866, USA. Electronic address: cdrucker@chapman.edu.
² Department of Chemistry and Biochemistry, James Madison University, 901 Carrier Drive, Harrisonburg, VA 22807, USA. Electronic address: cicaliar@dukes.jmu.edu.
³ Department of Chemistry and Biochemistry, James Madison University, 901 Carrier Drive, Harrisonburg, VA 22807, USA. Electronic address: rob24am@dukes.jmu.edu.
⁴ Department of Chemistry and Biochemistry, James Madison University, 901 Carrier Drive, Harrisonburg, VA 22807, USA. Electronic address: hugheyca@jmu.edu.
⁵ Food Science Program, Schmid College of Science and Technology, Chapman University, University Drive, Orange, CA 92866, USA. Electronic address: were@chapman.edu.

PMID: 37187006
DOI: 10.1016/j.foodchem.2023.136267

Abstract

Alkaline reactions of chlorogenic acid (CGA) yield undesirable development of brown or green pigments, limiting the utilization of alkalized CGA-rich foods. Thiols such as cysteine and glutathione mitigate pigment formation through several mechanisms, including redox coupling to reduce CGA quinones, and thiol conjugation, which forms colorless thiolyl-CGA compounds that do not readily participate in color-generating reactions. This work provided evidence of the formation of both aromatic and benzylic thiolyl-CGA conjugate species formed with cysteine and glutathione under alkaline conditions in addition to hydroxylated conjugate species hypothesized to arise from reactions with hydroxyl radicals. Formation of these conjugates proceeds more quickly than CGA dimerization and amine addition reactions mitigating pigment development. Differentiation between aromatic and benzylic conjugates is enabled by characteristic fragmentation of CS bonds. Acyl migration and hydrolysis of the quinic acid moiety of thiolyl-CGA conjugates yielded a variety of isomeric species also identified through untargeted LC-MS methods.

Keywords: Chlorogenic acid; Cysteine; Glutathione; LC-MS; Radical conjugation.

MeSH terms

Chlorogenic Acid* / chemistry
Cysteine* / chemistry
Glutathione / metabolism
Oxidation-Reduction
Sulfhydryl Compounds / chemistry

Substances

Cysteine
Chlorogenic Acid
Glutathione
Sulfhydryl Compounds