在水溶液中D-葡萄的酸盐催化降解伴随着C1-C2转换
Wenhui Zhang1, Anthony S Serianni
1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Journal of the American Chemical Society
|June 2, 2012
概括
D-葡萄糖的降解包括C1-C2键裂解,产生d-ribulose和formate. 无机酸盐催化了这一过程,其中可以包括C1-C2转化,这是糖分解的共同特征.
科学领域:
- 碳水化合物的化学成分
- 生物化学 生物化学
- 有机化学 有机化学
背景情况:
- 1,2-二碳基糖 (osones) 是碳水化合物代谢中的反应性中间体.
- 了解它们的降解途径对于阐明代谢过程和潜在的疾病机制至关重要.
研究的目的:
- 为了研究D-glucosone (D-arabino-hexos-2-ulose) 在水溶液中的降解途径.
- 阐明无机酸盐在D-葡萄降解中的作用,并确定新的反应机制.
主要方法:
- 使用了 (13) C 和 (1) H 核磁共振 (NMR) 谱学.
- 在详细的机理学研究中采用单和双 (13) C 标记的 D- 葡萄同位素.
- 在pH7.5和37°C的水性酸盐缓冲体中研究的降解,含有或不含酸盐或酸盐.
主要成果:
- 通过初始C1-C2键裂解,D-葡萄糖通过d-ribulose和formate降解,与其3-deoxy模拟物不同.
- 一种通过C3的化而形成的1,3-二乙烯基中间体,先于C1-C2键裂变.
- 在降解过程中意外观察到C1-C2转换,发生在约10%的转换中.
- 降解是由无机酸盐 (P) 和酸盐催化.
- 在D-xylosone中也观察到C1-C2转换,这表明它对于C3-氧化1,2-二碳酸糖是常见的.
结论:
- D-葡萄的降解通过一种新的途径进行,包括C1-C2键裂和潜在的C1-C2转移.
- 无机酸盐起着催化作用,可能是通过可逆酸盐 adduct 形成.
- 这些发现表明,P(i) 催化D-葡萄在体内分解可能涉及C1-C2转换.
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