Dependence of pyranose ring puckering on anomeric configuration: methyl idopyranosides.
Dependence of pyranose ring puckering on anomeric configuration: methyl idopyranosides.
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DOI：
10.1021/jp303183y
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发表时间：
2012-06-07
影响因子：
3.3
通讯作者：
Almond, Andrew
中科院分区：
文献类型：
--
作者：
Sattelle, Benedict M.;Bose-Basu, Bidisha;Tessier, Matthew;Woods, Robert J.;Serianni, Anthony S.;Almond, Andrew
在吡喃己醛糖艾杜糖中，三个轴环羟基的独特存在导致相当大的构象灵活性，使得实验研究具有挑战性，并且是合理化起皱和异头构型之间关系的极好模型。使用GLYCAM 11和三种显式水模型（TIP 3 P、TIP 4P和TIP 4P-EW）从动力学严格的10 μs模拟中预测甲基α-和β-l-艾杜吡喃糖苷的起皱。在每种情况下，计算的吡喃糖环三键（邻位）1H-1H自旋耦合（3 JH，H）与NMR测量的趋势。这些值，计算的起皱交换率和自由能是独立的水模型。α-和β-端基异构体分别有85%和>99%的轨道是1C 4椅，并以20 μs-1和1 μs-1的速率进行1C 4 → 4C 1交换。计算的α-端基异构体1C 4 Participate 4C 1起皱速率依赖于环外C6取代基，比较羟甲基与羧基从以前的工作。β-异头物的较慢动力学和受限的假旋转曲线是由于水占据由异头物1-O-甲基和C6羟甲基界定的空腔所致。这一发现使不同的甲基α-和β-l-吡喃艾杜糖甙3 JH，H值合理化。确定吡喃艾杜糖异头构型、μ s-起皱和水结构之间的关系有助于生物学和商业上重要的衍生物的工程化，并支持破译糖组中目前难以理解的结构-功能关系。
In the aldohexopyranose idose, the unique presence of three axial ring hydroxyl groups causes considerable conformational flexibility, rendering it challenging to study experimentally and an excellent model for rationalising the relationship between puckering and anomeric configuration. Puckering in methyl α- and β-l-idopyranosides was predicted from kinetically rigorous 10 μs simulations using GLYCAM11 and three explicit water models (TIP3P, TIP4P and TIP4P-EW). In each case, computed pyranose ring three-bond (vicinal) 1H-1H spin-couplings (3JH,H) trended with NMR measurements. These values, calculated puckering exchange rates and free energies were independent of the water model. The α- and β-anomers were 1C4 chairs for 85% and >99% of their respective trajectories and underwent 1C4→4C1 exchange at rates of 20 μs-1 and 1 μs-1. Computed α-anomer 1C4↔4C1 puckering rates depended on the exocyclic C6 substituent, comparing hydroxymethyl with carboxyl from previous work. The slower kinetics and restricted pseudorotational profile of the β-anomer were caused by water occupying a cavity bounded by the anomeric 1-O-methyl and the C6 hydroxymethyl groups. This finding rationalises the different methyl α- and β-l-idopyranoside 3JH,H values. Identifying a relationship between idopyranose anomeric configuration, μs-puckering and water structure facilitates engineering of biologically and commercially important derivatives and underpins deciphering presently elusive structure-function relationships in the glycome.
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影响因子：
5.5
作者：
Hess, Berk;Kutzner, Carsten;Lindahl, Erik
通讯作者：
Lindahl, Erik
影响因子：
2.1
作者：
HAASNOOT, CAG;DELEEUW, FAAM;ALTONA, C
通讯作者：
ALTONA, C
影响因子：
4.3
作者：
Sattelle BM;Almond A
通讯作者：
Almond A
DOI：
10.1039/jr9630005350
发表时间：
1963-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY
影响因子：
--
作者：
AUSTIN, PW;BADDILEY, J;BUCHANAN, JG
通讯作者：
BUCHANAN, JG
影响因子：
15
作者：
Sattelle, Benedict M.;Hansen, Steen U.;Almond, Andrew
通讯作者：
Almond, Andrew