NMR Verification of Structures of Bacterial Saccharide Precursors for Vaccines

用500 MHz核磁共振谱研究了宋内志贺菌O-特异性多糖（O-SP）的3个组分，并用2D COSY、HSQC和TOCSY方法，结合1D ~ 1H和~（13）C核磁共振谱，以及~ 1H-偶合~（13）C核磁共振谱对糖残基的异头构型进行了确证。 已检查了用于制备霍乱弧菌结合疫苗的约40批单糖中间体和连接体的300 MHz 1H NMR光谱，以确保正确解释和真实性。光谱分散度（NMR光谱的扩展）和光谱分辨率（共振的窄度）限于300 MHz，因此霍乱弧菌中间体的NMR数据由10组在500 MHz测量的1H和/或13 C NMR数据补充。这些光谱提供了比300 MHz NMR光谱更详细的结构信息和光谱归属，例如，检测小的长程1H 1H耦合常数（如果存在）。 肺炎克雷伯氏菌2型荚膜多糖的5个色谱级分的结构已通过500 MHz的高分辨率NMR光谱进行表征，包括使用1H NMR、13 C NMR和2D杂原子单量子相关（HSQC）NMR来关联和分配1H和13 C化学位移。NMR光谱提供了有关结构的一般类型及其纯度的信息，并与相关材料的文献数据进行了比较。

Three fractions of the O-specific polysaccharide(O-SP) isolated from Shigella sonnei have been investigated by NMR at 500 MHz, and the structure of the polysaccharide verified by 2D COSY, HSQC, and TOCSY methods, in conjunction with 1D 1H and 13C NMR, and 1H-coupled 13C NMR for confirmation of the anomeric configuration of the sugar residues. The 300 MHz 1H NMR spectra of about 40 batches of monosaccharide intermediates and linkers directed towards preparation of a conjugate vaccine for Vibrio cholera have been inspected for correct interpretation and authenticity. The degree of spectral dispersion (spreading of the NMR spectrum) and spectral resolution (narrowness of the resonances) is limited at 300 MHz, so the NMR data for the Vibrio cholera intermediates have been supplemented by 10 sets of 1H and/or 13C NMR data measured at 500 MHz. These spectra provide more detailed structural information and spectral assignments than are available from 300 MHz NMR spectra, for example, the detection of small, long-range 1H1H coupling constants, if present. The structures of five chromatographic fractions of Klebsiella pneumoniae type 2 capsular polysaccharide have been characterized by high-resolution NMR spectroscopy at 500 MHz, including the use of 1H NMR, 13C NMR, and 2D heteronuclear single quantum correlation (HSQC) NMR to correlate and assign the 1H and 13C chemical shifts. The NMR spectra provided information on the general types of structures involved and their purity, and afforded comparisons with literature data for related materials.