Wu Ruiying, Richter Stefan, Zhang Rong-guang, Anderson Valerie J, Missiakas Dominique, Joachimiak Andrzej
Biosciences Division, Midwest Center for Structural Genomics and Structural Biology Center, Argonne National Laboratory, Argonne, Illinois 60439, USA.
J Biol Chem. 2009 Sep 4;284(36):24406-14. doi: 10.1074/jbc.M109.019034. Epub 2009 Jun 16.
Bacillus anthracis elaborates a poly-gamma-d-glutamic acid capsule that protects bacilli from phagocytic killing during infection. The enzyme CapD generates amide bonds with peptidoglycan cross-bridges to anchor capsular material within the cell wall envelope of B. anthracis. The capsular biosynthetic pathway is essential for virulence during anthrax infections and can be targeted for anti-infective inhibition with small molecules. Here, we present the crystal structures of the gamma-glutamyltranspeptidase CapD with and without alpha-l-Glu-l-Glu dipeptide, a non-hydrolyzable analog of poly-gamma-d-glutamic acid, in the active site. Purified CapD displays transpeptidation activity in vitro, and its structure reveals an active site broadly accessible for poly-gamma-glutamate binding and processing. Using structural and biochemical information, we derive a mechanistic model for CapD catalysis whereby Pro(427), Gly(428), and Gly(429) activate the catalytic residue of the enzyme, Thr(352), and stabilize an oxyanion hole via main chain amide hydrogen bonds.
炭疽芽孢杆菌可产生一种多聚 -γ -d -谷氨酸荚膜,在感染期间保护杆菌免受吞噬杀伤。CapD酶与肽聚糖交联桥形成酰胺键,从而将荚膜物质锚定在炭疽芽孢杆菌的细胞壁包膜内。荚膜生物合成途径在炭疽感染期间对毒力至关重要,并且可以成为小分子抗感染抑制的靶点。在此,我们展示了γ -谷氨酰转肽酶CapD在活性位点结合和不结合α -l -Glu -l -Glu二肽(一种多聚 -γ -d -谷氨酸的非水解类似物)时的晶体结构。纯化的CapD在体外表现出转肽活性,其结构揭示了一个可广泛结合和加工多聚 -γ -谷氨酸的活性位点。利用结构和生化信息,我们推导了CapD催化的机制模型,即Pro(427)、Gly(428)和Gly(429)激活酶的催化残基Thr(352),并通过主链酰胺氢键稳定氧负离子洞。