<\/p>\n
Enzymes are nature\u2019s tools for catalyzing life\u2019s essential reactions. Though unrivaled in their efficiency and selectivity, enzymes only carry out a narrow range of natural reactions, limiting their usefulness in modern organic synthesis. Now, Princeton researchers report a method that expands the realm of enzyme reactivity to a non-natural reaction and allows organic chemists to access the high selectivities offered by enzymes. <\/p>\n
Published in Nature<\/em> and led by assistant professor of chemistry Todd Hyster, the work is the first example of a reaction that employs light to activate new reactivity in an existing enzyme. The research team targeted a family of enzymes called ketoreductases that traditionally transform ketones to alcohols. Ketoreductases are dependent on a co-factor, or molecule commonly present to help drive enzyme-catalyzed reactions forward, called nicotinamide, which is known to respond to light.<\/p>\n Using a commercial kit from the company Codexis, the researchers irradiated a variety of proteins from the ketoreductase family to see if they could instead steer the chemical pathway towards a different reactivity. \u201cThese kits are a nice starting point for finding out whether your reactivity has a shot or not,\u201d Hyster said. \u201cIt really accelerated our discovery process,\u201d Hyster said.<\/p>\n Their investigations revealed that photo-excited nicotinamide-dependent ketoreductases successfully catalyzed a dehalogenation reaction, in which a halogen atom is replaced with a hydrogen atom, to produce a variety of chiral, or geometrically distinct, small molecules called lactones. <\/p>\n Through subsequent, minor mutations of the enzyme, the researchers were able to reach high reaction efficiencies and selectivities. They proposed that the good reactivity arises from a charge transfer complex and the selectivity owes to the key intermediate binding within the active site of the enzyme.<\/p>\n The reaction showed that enzymes can be coaxed to perform new chemistry and in the future Hyster\u2019s team hopes to apply their methodology to even more synthetically challenging reactions.<\/p>\n ###<\/p>\n \t<\/strong><\/p>\n Read the full article here:<\/p>\n<\/p>\n Emmanuel, M. A.; Greenberg, N. R.; Oblinsky, D. G.; Hyster, T. K. \u201cAccessing non-natural reactivity by irradiating nicotinamide-dependent enzymes with light.\u201d Nature<\/em> 2016 540, 414.<\/p>\n","protected":false},"excerpt":{"rendered":" Enzymes are nature\u2019s tools for catalyzing life\u2019s essential reactions. Though unrivaled in their efficiency and selectivity, enzymes only carry out a narrow range of natural reactions, limiting their usefulness in modern organic synthesis. Now, Princeton researchers report a method that expands the realm of enzyme reactivity to a non-natural reaction and allows organic chemists to […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[],"tags":[],"class_list":["post-60267","post","type-post","status-publish","format-standard","hentry"],"_links":{"self":[{"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/posts\/60267","targetHints":{"allow":["GET"]}}],"collection":[{"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/comments?post=60267"}],"version-history":[{"count":0,"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/posts\/60267\/revisions"}],"wp:attachment":[{"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/media?parent=60267"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/categories?post=60267"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/healthmedicinet.com\/news\/wp-json\/wp\/v2\/tags?post=60267"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}