分析 UDP-D-岩藻糖/ UDP-D-木糖合酶催化 UDP-D-岩藻糖磷酸酯向 UDP-D-木糖磷酸酯的转化：对 retroaldol-aldol 机制的启示。
Analysis of UDP-D-apiose/UDP-D-xylose synthase-catalyzed conversion of UDP-D-apiose phosphonate to UDP-D-xylose phosphonate: implications for a retroaldol-aldol mechanism.
机构信息
Division of Medicinal Chemistry, College of Pharmacy, and Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
出版信息
J Am Chem Soc. 2012 Aug 29;134(34):13946-9. doi: 10.1021/ja305322x. Epub 2012 Aug 15.
Abstract
UDP-D-apiose/UDP-D-xylose synthase (AXS) catalyzes the conversion of UDP-D-glucuronic acid to UDP-D-apiose and UDP-D-xylose. An acetyl-protected phosphonate analogue of UDP-D-apiose was synthesized and used in an in situ HPLC assay to demonstrate for the first time the ability of AXS to interconvert the two reaction products. Density functional theory calculations provided insight into the energetics of this process and the apparent inability of AXS to catalyze the conversion of UDP-D-xylose to UDP-D-apiose. The data suggest that this observation is unlikely to be due to an unfavorable equilibrium but rather results from substrate inhibition by the most stable chair conformation of UDP-D-xylose. The detection of xylose cyclic phosphonate as the turnover product reveals significant new details about the AXS-catalyzed reaction and supports the proposed retroaldol-aldol mechanism of catalysis.
摘要
UDP-D-阿洛酮糖/UDP-D-木酮糖合酶（AXS）催化 UDP-D-葡萄糖醛酸转化为 UDP-D-阿洛酮糖和 UDP-D-木酮糖。合成了 UDP-D-阿洛酮糖的乙酰保护膦酸酯类似物，并在原位 HPLC 测定中首次证明了 AXS 能够相互转化两种反应产物的能力。密度泛函理论计算提供了对该过程能量学的深入了解，以及 AXS 似乎不能催化 UDP-D-木酮糖转化为 UDP-D-阿洛酮糖的原因。数据表明，这种观察结果不太可能是由于不利的平衡，而是由于 UDP-D-木酮糖最稳定的椅式构象对底物的抑制作用所致。木糖环状膦酸酯作为周转产物的检测揭示了 AXS 催化反应的重要新细节，并支持了所提出的催化反醛-醛醇机制。
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Chem Commun (Camb). 2011 Sep 28;47(36):10130-2. doi: 10.1039/c1cc13140k. Epub 2011 Aug 9.
2
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Carbohydr Res. 2009 Jun 12;344(9):1072-8. doi: 10.1016/j.carres.2009.03.026. Epub 2009 Mar 27.
3
Developmental Control of Apiogalacturonan Biosynthesis and UDP-Apiose Production in a Duckweed.浮萍中果胶寡糖生物合成和 UDP-阿比糖产生的发育调控
Plant Physiol. 1989 Jul;90(3):972-6. doi: 10.1104/pp.90.3.972.
4
Characterization of protein encoded by spnR from the spinosyn gene cluster of Saccharopolyspora spinosa: mechanistic implications for forosamine biosynthesis.来自多刺糖多孢菌的多杀菌素基因簇的spnR编码蛋白的特性：福乐糖胺生物合成的机制意义
J Am Chem Soc. 2005 Jun 1;127(21):7692-3. doi: 10.1021/ja042702k.
5
Synthesis of mono- and disaccharide analogs of moenomycin and lipid II for inhibition of transglycosylase activity of penicillin-binding protein 1b.用于抑制青霉素结合蛋白1b转糖基酶活性的莫能菌素和脂质II单糖及二糖类似物的合成。
Bioorg Med Chem. 2004 Dec 15;12(24):6473-94. doi: 10.1016/j.bmc.2004.09.019.
6
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7
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10
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