自从2001年丝氨酸八聚体第一次在质谱中被观察到,这种奇特的幻数团簇就受到研究者们的广泛关注。丝氨酸八聚体具有显著的同手性优势,而且它的手性能够通过对映选择性取代反应传递给其他分子。一些研究者提出这种丝氨酸八聚体的同手性优势很可能与生命的同手性起源相关。本文综述了丝氨酸八聚体的产生、结构和手性特征等方面的研究结果和进展,其中包括运用串联质谱(MS/MS),气相H/D交换,离子淌度,红外解离光谱等多种实验方法以及理论计算对丝氨酸八聚体及含有取代单元的八聚体的相关研究。这些结果逐步地揭示了丝氨酸八聚体的结构特点和性质,进一步加深了人们对其在手性识别和手性传递方面的作用的理解。然而,由于体系的复杂性,真正地理解其结构、同手性选择性的原因以及其在生物分子同手性起源中的作用仍是一个非常具有挑战性的问题。
Serine octamer as a unique “magic-number” cluster in the gas phase, has been extensively studied by experimentalists and theorists since its discovery in mass spectrometry in 2001. It is characterized by a pronounced preference of homochirality. Interestingly, the chirality of serine octamer can transfer to other molecules through enantioselective substitution reactions. Thus it is suggested that it might be related to the origin of our homochiral world. In this review, all the results and progresses in the formation, structure and chiral signature of serine octamer and substituted serine octamer over the past years are summarized. Different methods, including mass spectrometry with different ionization sources, gas phase H/D exchange, ion mobility, infrared photodissociation spectroscopy, and theoretical calculations are applied for the cluster ions. Different characteristics of the magic cluster are discovered gradually, helping us to have a deep insight into its structure and role in chiral recognition and transmission. However, due to the complexity of the system, it is still a big challenge to understand its true structure, the reason of its performance in homochirality and its role in the origin of biomolecular homochirality.
Contents
1 Introduction
2 Generation of serine octamer
2.1 Electrospray
2.2 Other spray-based ionization method
2.3 Evaporation and sublimation
2.4 Other method
2.5 Mechanism
3 Structural studies
3.1 MS/MS
3.2 Gas-phase H/D exchange
3.3 Ion mobility
3.4 IRPD spectroscopy
3.5 Theoretical calculation
4 Substituted serine octamers
4.1 Substituted by other amino acids
4.2 Substituted by sugars
4.3 Other relative clusters
5 Chiral characteristic
5.1 Enantiometic enrichment and chiral transmission
5.2 Chiral differentiation
5.3 Discussion
6 Conclusion
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