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Controlled self-assembling structures of ferrocene-dipeptide conjugates composed of Ala-Pro-NHCH2CH2SH chain
Journal of Inorganic Biochemistry ( IF 3.9 ) Pub Date : 2017-05-18 , DOI: 10.1016/j.jinorgbio.2017.05.009
Toshiyuki Moriuchi , Taiki Nishiyama , Yoshiki Tayano , Toshikazu Hirao

Bioorganometallic ferrocene-dipeptide conjugates with the Ala-Pro-cysteamine chain, Fc-L-Ala-L-Pro-NHCH2CH2SH (2) and Fc-L-Ala-D-Pro-NHCH2CH2SH (4) (Fc = ferrocenoyl), were prepared by the reduction of the ferrocene-dipeptide conjugates, Fc-L-Ala-L-Pro-cystamine-L-Pro-L-Ala-Fc (1) or Fc-L-Ala-D-Pro-cystamine-D-Pro-L-Ala-Fc (3), respectively. Control of the self-assembling structures of the ferrocene-dipeptide conjugates was demonstrated by changing the chirality of the amino acid. The molecular structure of 2 composed of the L-Ala-L-Pro-NHCH2CH2SH chain confirmed the formation of intramolecular hydrogen bond of N-H ⋯ N pattern between the NH of cysteamine moiety and the nitrogen of Pro moiety. Furthermore, intermolecular hydrogen bonds between NH (Ala) and CO (Pro of another molecule) and between NH (cysteamine) and CO (the ferrocenoyl moiety of another molecule) were formed, wherein each molecule is connected to four neighboring molecules by continuous intermolecular hydrogen bonds to form the hydrogen-bonded molecular assembling structure. On the contrary, the left-handed helical assembly through an intermolecular hydrogen-bonding network of 15-membered intermolecularly hydrogen-bonded ring between NH (Ala) and CO (the ferrocenoyl moiety of another molecule) and between NH (the cysteamine moiety of another molecule) and CO (Ala) was observed in the crystal packing of 4 composed of the L-Ala-D-Pro-NHCH2CH2SH chain.



中文翻译:

由Ala-Pro-NHCH 2 CH 2 SH链组成的二茂铁-二肽共轭物的受控自组装结构

具有Ala-Pro-半胱胺链,Fc-L-Ala-L-Pro-NHCH 2 CH 2 SH(2)和Fc-L-Ala-D-Pro-NHCH 2 CH 2 SH(4)(Fc =二茂铁酰基),是通过还原二茂铁-二肽共轭物,Fc-L-Ala-L-Pro-胱氨酸-L-Pro-L-Ala-Fc(1)或Fc-L-Ala- D-胱氨酸胺-D-Pro-L-Ala-Fc(3)。通过改变氨基酸的手性证明了对二茂铁-二肽缀合物的自组装结构的控制。由L-Ala-L-Pro-NHCH 2 CH 2组成的2的分子结构SH链证实了半胱胺部分的NH和Pro部分的氮之间形成NH⋯N型分子内氢键。此外,在NH(Ala)和CO(另一个分子的Pro)之间以及在NH(半胱胺)和CO(另一个分子的二茂铁基部分)之间形成了分子间氢键,其中每个分子通过连续的分子间氢与四个相邻分子连接键形成氢键分子组装结构。相反,在NH(Ala)与CO(另一个分子的二茂铁基部分)之间以及NH(另一个分子的半胱胺部分)之间的15元分子间氢键合环的分子间氢键网络中,左手螺旋组装分子)和一氧化碳(Ala)的晶体堆积中观察到4将L-ALA-d-PRO-NHCH组成2 CH 2 SH链。

更新日期:2017-05-18
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