通过18-皇冠-6对氨基酸的分子识别中的结构和能量效应
1Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
Journal of the American Chemical Society
|March 10, 2012
概括
这项研究使用质谱学量化了五种氨基酸 (AAs) 的18-皇冠-6 (18C6) 亲和关系. 结果显示了不同的结合亲和力,这对生物系统中的18C6复合有影响.
科学领域:
- 分析化学 分析化学
- 计算化学计算化学
- 生物化学 生物化学
背景情况:
- 氨基酸 (AAs) 是基本的生物构建块.
- 18-皇冠-6 (18C6) 是一种以其结合阳离子的能力而闻名的宏环乙烯.
- 了解18C6和AA之间的相互作用对于研究生物系统中的复杂化至关重要.
研究的目的:
- 确定五种氨基酸的绝对18皇冠-6 (18C6) 亲和关系:甘氨酸,氨酸,氨酸,氨酸,氨酸和氨酸.
- 研究中性和质子18C6和AA复合物的理论电子结构和能量.
- 为了将实验的结合亲和关系与理论计算相关联,并探索对生物复杂化的影响.
主要方法:
- 导向离子束双重质谱法被用来测量绝对的18C6亲和度.
- 进行了理论电子结构计算 (M06和B3LYP),以确定稳定的几何和能量.
- 碰撞诱导解离 (CID) 用于分析与质子结合的AA-18C6复合体的碎片化模式.
主要成果:
- 甘氨酸和氨酸的质子亲和度低于18C6,而氨酸,氨酸和氨酸超过了它.
- CID的实验揭示了基于AA质子亲和力的独特碎片化路径.
- M06理论与实验性键解离能很好地一致,除了希斯蒂丁复合物.
结论:
- 氨酸在基本的AA中表现出最高的结合亲和力,这表明其侧链是和蛋白质中首选的结合点.
- 甘氨酸和氨酸比氨酸具有更大的18C6结合亲和力,这表明N端氨基群也是一个有利的结合位点.
- 18C6结合亲和度与AA极化性和质子亲和度相反相关,N端结合对甘氨酸最有利.
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