Journal
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-CRYSTALLINE MATERIALS
Volume 233, Issue 8, Pages 531-537Publisher
WALTER DE GRUYTER GMBH
DOI: 10.1515/zkri-2018-2064
Keywords
FAD; flavoenzymes; sigma-hole; lone-pair center dot center dot center dot pi interactions; oxidoreductases; sulfur
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Funding
- National Council for Scientific and Technological Development [CNPq-308480/2016-3, CNPq-457255/2014-5, 305626/2013-2]
- Coordination for the Improvement of Higher Education Personnel (CAPES)
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The interactions of pi-systems with lone-pairs of electrons are known and have been described in biological systems, involving lone-pairs derived from metals, metalloids, sulfur, oxygen and nitrogen. This study describes a bibliographic survey of the disulfide-bound sulfur(lone-pair) interactions with pi-systems residing in the flavin adenine dinucleotide (FAD) cofactor of oxidoreductase enzymes (flavoenzymes). Thus, of the 172 oxidoreductase enzymes evaluated for gamma-S(lone-pair)center dot center dot center dot pi(FAD) interactions, 96 proteins (56%) exhibited these interactions corresponding; 61% of 350 the constituent monomers featured at least one gamma-S(lone-pair)center dot center dot center dot pi(FAD) interaction. Two main points of association between the S(lone-pair) and the isoalloxazine moiety of FAD were identified, namely at the centroid of the bond linking the uracil and pyrazine rings (60%), and the centroid of the uracil ring (37%). Reflecting the nature of the secondary structure in three prominent classes of oxidoreductase enzymes: glutathione disulfide reductases (GR; 21 proteins), trypanothione disulfide reductases (TR, 14) and sulfhydryl oxidases (SOX, 22), the approach of the gamma-S(lone-pair) to the FAD residue was to the si-face of the isoalloxazine ring system, i.e. to the opposite side as the carbonyl residue, for all GR and TR examples, and to the re-face for all SOX examples. Finally, the attractive nature of the gamma-S(lone-pair)center dot center dot center dot pi(FAD) interactions was confirmed qualitatively by an examination of the non-covalent interaction plots.
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