% IMPORTANT: The following is UTF-8 encoded. This means that in the presence % of non-ASCII characters, it will not work with BibTeX 0.99 or older. % Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or % “biber”. @ARTICLE{Gruber:491728, author = {Gruber, Karl and Csitkovits, Vanessa and Łyskowski, Andrzej and Kratky, Christoph and Kräutler, Bernhard}, title = {{S}tructure‐{B}ased {D}emystification of {R}adical {C}atalysis by a {C}oenzyme {B}$_{12}$ {D}ependent {E}nzyme—{C}rystallographic {S}tudy of {G}lutamate {M}utase with {C}ofactor {H}omologues}, journal = {Angewandte Chemie}, volume = {134}, number = {35}, issn = {0932-2132}, address = {Weinheim}, publisher = {Wiley-VCH}, reportid = {PUBDB-2023-00367}, pages = {e202208295}, year = {2022}, abstract = {Catalysis by radical enzymes dependent on coenzyme B$_{12}$ (AdoCbl) relies on the reactive primary 5′-deoxy-5′adenosyl radical, which originates from reversible Co−C bond homolysis of AdoCbl. This bond homolysis is accelerated roughly 10$^{12}$-fold upon binding the enzyme substrate. The structural basis for this activation is still strikingly enigmatic. As revealed here, a displaced firm adenosine binding cavity in substrate-loaded glutamate mutase (GM) causes a structural misfit for intact AdoCbl that is relieved by the homolytic Co−C bond cleavage. Strategically interacting adjacent adenosine- and substrate-binding protein cavities provide a tight caged radical reaction space, controlling the entire radical path. The GM active site is perfectly structured for promoting radical catalysis, including “negative catalysis”, a paradigm for AdoCbl-dependent mutases.}, cin = {DOOR ; HAS-User}, ddc = {660}, cid = {I:(DE-H253)HAS-User-20120731}, pnm = {899 - ohne Topic (POF4-899)}, pid = {G:(DE-HGF)POF4-899}, experiment = {EXP:(DE-H253)D-BW7-20150101}, typ = {PUB:(DE-HGF)16}, doi = {10.1002/ange.202208295}, url = {https://bib-pubdb1.desy.de/record/491728}, }