1H, 13C, and 31P nuclear magnetic resonance spectral assignments for tobramycin, 2''-(adenosine-5'-phosphoryl)-tobramycin and 2''-(adenosine-5'-thiophosphoryl)-tobramycin.
1H, 13C, and 31P nuclear magnetic resonance spectral assignments for tobramycin, 2''-(adenosine-5'-phosphoryl)-tobramycin and 2''-(adenosine-5'-thiophosphoryl)-tobramycin.
复制标题
妥布霉素、2-(腺苷-5-磷酰基)-妥布霉素和2-(腺苷-5-硫代磷酰基)-妥布霉素的1H、13C和31P核磁共振谱归属。
DOI：
10.1016/0003-9861(90)90331-r
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发表时间：
1990
影响因子：
3.9
通讯作者：
Frey,PA
中科院分区：
文献类型：
--
作者：
VanPelt,JE;Mooberry,ES;Frey,PA
利用庆大霉素核苷基转移酶催化妥布霉素腺苷化，以ATP和(Sp)-ATPαS为底物，制备了妥布霉素的两个酶修饰衍生物。(EC 2.7.7.46)。1h，13C和31p NMR谱被分配给妥布霉素，2″-（腺苷-5 ' -磷酰）-妥布霉素（TbAMP）和2″-（腺苷-5 ' -硫磷酰）-妥布霉素（TbAMPS）。已经使用了几种一维和二维核磁共振技术，值得注意的是，470或500 MHz的1H同核相关光谱和50.3 MHz的13c1H异核相关光谱。妥布霉素的1h配位与之前报道的卡那霉素a的环I和环III相似。妥布霉素的13c配位与之前报道的相似，只是糖基环上的头基碳的配位发生了反转。妥布霉素的1h和13c赋值用于指导TbAMP和TbAMPS的光谱赋值。这两种妥布霉素衍生物几乎得到了完整的配位。从测量的质子偶联常数来看，妥布霉素经腺苷化修饰后，只有很小的构象变化。从腺苷化衍生物的质子和碳谱图可以看出，2″的位置是腺苷化的位点。2″质子和碳共振的大下场位移很容易被观察到，并且在TbAMPS中比TbAMP更明显。
Two enzymatically modified derivatives of tobramycin have been prepared by gentamicin nucleotidyl transferase-catalyzed adenylylation of tobramycin, using ATP and (Sp)-ATPαS as adenylylation substrates. (EC 2.7.7.46). The1H,13C, and31P NMR spectra have been assigned for tobramycin, 2″-(adenosine-5′-phosphoryl)-tobramycin (TbAMP) and 2″-(adenosine-5′-thiophosphoryl)-tobramycin (TbAMPS). Several one -and two-dimensional NMR techniques have been utilized, notably,1H1H homonuclear correlation spectroscopy at 470 or 500 MHz and13C1H heteronuclear correlation spectroscopy at 50.3 MHz. The1H assignments for tobramycin are similar to those previously reported for rings I and III of kanamycin A. The13C assignments for tobramycin were similar to those previously reported, except for reversal of the assignments for anomeric carbons in the glycosyl rings.The1H and13C assignments for tobramycin were used to guide the assignments of the spectra for TbAMP and TbAMPS. Nearly complete assignments were obtained for these two derivatives of tobramycin. From the measured proton coupling constants, only small conformational changes were observed upon modification of tobramycin by adenylylation. From the proton and carbon spectra of the adenylylated derivatives the 2″ position is shown to be the site of adenylation. Large downfield shifts of the 2″ proton and carbon resonances are easily observed and are more pronounced for TbAMPS than for TbAMP.