用于模拟三维核欧沃豪斯效应（NOE）-核欧沃豪斯效应光谱的精确方法与近似方法

Exact vs approximate methods for simulation of 3D NOE-NOE spectra.

作者信息

Donne D G, Gozansky E K, Gorenstein D G

机构信息

Department of Chemistry, Purdue University, West Lafayette, Indiana 47907.

出版信息

J Magn Reson B. 1995 Feb;106(2):156-63. doi: 10.1006/jmrb.1995.1026.

DOI:10.1006/jmrb.1995.1026

PMID:7850183

Abstract

An exact full matrix analysis of 2D NOESY spectroscopy has been extended to 3D homonuclear NOE-NOE spectroscopy and applied to the simulation of NOE-NOE spectra of the Dickerson dodecamer d(CGCGAATTCGCG)2 and a tandem GA mismatched decamer deoxynucleotide duplex d(CCAAGATTGG)2. The exact method has been compared with the approximation method based on Taylor expansions. It has been found that the approximations using one or two terms in the Taylor expansion series are generally inadequate for simulations of 3D NOE-NOE volumes and fail at very short mixing times, depending on the motional properties of the biomolecule in question. Specifically, the first-order approximation fails at tau c tau m > or = 1.8 x 10(-10) s2 for both the dodecamer and the decamer if an RMS error in the volumes of < 50% is desired.

摘要

二维核Overhauser效应光谱（2D NOESY）的精确全矩阵分析已扩展至三维同核核Overhauser效应-核Overhauser效应光谱（3D homonuclear NOE-NOE），并应用于Dickerson十二聚体d(CGCGAATTCGCG)₂和串联GA错配十聚体脱氧核苷酸双链体d(CCAAGATTGG)₂的NOE-NOE光谱模拟。已将该精确方法与基于泰勒展开的近似方法进行比较。结果发现，在泰勒展开级数中使用一项或两项的近似通常不足以模拟三维NOE-NOE体积，并且在非常短的混合时间下会失效，这取决于所研究生物分子的运动特性。具体而言，如果希望体积的均方根误差小于50%，则对于十二聚体和十聚体，当相关时间（τc）与混合时间（τm）的乘积大于或等于1.8×10⁻¹⁰ s²时，一阶近似会失效。