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Enzymes canusually be unambiguously assigned to one of seven classes specifying the basic chemistry of their catalyzed reactions. Less frequently, two or more reaction classes are catalyzed by a single enzyme within one active site. Two examples are an isomerohydrolase and an isomero-oxygenase that catalyze isomerization-coupled reactions crucial for production of visionsupporting 11-cis-retinoids. In these enzymes, isomerization is obligately paired and mechanistically intertwined with a second reaction class. A handful of other enzymes carrying out similarly coupled isomerization reactions have been described, some ofwhich havebeensubjectedtodetailedstructure–function analyses. Herein we reviewtheserarefied enzymes,focusingonthe mechanisticand structural basis of their reaction coupling with the goal of revealing catalytic commonalities.more » « less
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