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Reaction mechanisms of TK, PK, and acetyl-P-producing POX. The first-half reactions of XFPK and TK are identical, but the second-half- reactions diverge. The reaction catalyzed by POX involves oxidation and radical chemistry. Pyr represents the aminopyrimidine ring of ThDP. Protonated DHEThDP (S-α,β-dihydroxyethyl-ThDP), which is likely the state observed in our crystal structure, is also shown.
