Mineo Placido, Vitalini Daniele, La Mendola Diego, Rizzarelli Enrico, Scamporrino Emilio, Vecchio Graziella
Istituto di Chimica e Tecnologia dei Polimeri, CNR-Sezione di Catania, Catania, Viale A. Doria, 6, Catania 95125, Italy.
J Inorg Biochem. 2004 Feb;98(2):254-65. doi: 10.1016/j.jinorgbio.2003.10.015.
The synthesis and characterization of two beta-cyclodextrins (beta-CD) functionalized with two units of carnosine (beta-alanyl-L-histidine) through the amino group, 6A,6C-(beta-alanyl-L-histidine)-6A,6C-dideoxy-beta-cyclodextrin (ACCDAH) and 6A,6D-(beta-alanyl-L-histidine)-6A,6D-dideoxy-beta-cyclodextrin (ADCDAH), are reported. NMR and C.D. data of the ligands indicate a different interaction of dipeptide chains with upper rim and cavity of beta-CD. Analogously, spectroscopic and electrospray ionization mass spectrometry data show different copper(II) complex species formed by the two regioisomers. The ability of carnosine-cyclodextrin derivatives to bind copper ions in a head-to-tail fashion induces the formation of oligomeric species (up to hexamers) in the case of ACCDAH, where the two carnosine moieties are adjacent, while in the ADCDAH case the mutual interaction between the peptidic chains of two ADCDAH molecules allows the almost exclusive formation of a copper-assisted self-assembled dimeric species.
报道了通过氨基将两个肌肽（β-丙氨酰-L-组氨酸）单元功能化的两种β-环糊精（β-CD）的合成与表征，即6A,6C-（β-丙氨酰-L-组氨酸）-6A,6C-二脱氧-β-环糊精（ACCDAH）和6A,6D-（β-丙氨酰-L-组氨酸）-6A,6D-二脱氧-β-环糊精（ADCDAH）。配体的核磁共振和圆二色光谱数据表明二肽链与β-环糊精的上缘和空腔存在不同的相互作用。类似地，光谱和电喷雾电离质谱数据显示这两种区域异构体形成了不同的铜（II）络合物物种。肌肽-环糊精衍生物以头对尾方式结合铜离子的能力，在ACCDAH（其中两个肌肽部分相邻）的情况下诱导形成寡聚体物种（高达六聚体），而在ADCDAH的情况下，两个ADCDAH分子的肽链之间的相互作用几乎排他性地形成了一种铜辅助的自组装二聚体物种。
