Di-heterometalation of thiol-functionalized peptide nucleic acids.

Tanmaya Joshi, Malay Patra, Leone Spiccia, Gilles Gasser
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Abstract

As a proof-of-principle, two hetero-bimetallic PNA oligomers containing a ruthenium(II) polypyridyl and a cyclopentadienyl manganese tricarbonyl complex have been prepared by serial combination of solid-phase peptide coupling and in-solution thiol chemistry. Solid-phase N-terminus attachment of Ru(II)-polypyridyl carboxylic acid derivative, C1, onto the thiol-functionalized PNA backbone (H-a-a-g-t-c-t-g-c-linker-cys-NH 2) has been performed by standard peptide coupling method. As two parallel approaches, the strong affinity of thiols for maleimide and haloacetyl group has been exploited for subsequent post-SPPS addition of cymantrene-based organometallic cores, C2 and C3. Michael-like addition and thioether ligation of thiol functionalized PNA1 (H-gly-a-a-g-t-c-t-g-c-linker-cys-NH 2) and PNA2 (C1-a-a-g-t-c-t-g-c-linker-cys-NH 2) to cymantrene maleimide and chloroacetyl derivatives, C2 and C3, respectively, has been performed. The synthesized ruthenium(II)-cymantrenyl PNA oligomers have been characterized by mass spectrometry (ESI-MS) and IR spectroscopy. The distinct Mn-CO vibrational IR stretches, between 1,924-2,074 cm (-1) , have been used as markers to confirm the presence of cymantrenyl units in the PNA sequences and the purity of the HPLC-purified PNA thioethers assessed using LC-MS.

巯基功能化肽核酸的二氢化。
作为原理验证,我们通过固相肽偶联和溶液中硫醇化学的连续组合,制备出了两种含有多吡啶基钌(II)和环戊二烯基三羰基锰络合物的异质双金属 PNA 低聚物。通过标准的肽偶联方法,Ru(II)-聚吡啶基羧酸衍生物 C1 在硫醇官能化的 PNA 骨架(H-a-a-g-t-c-t-g-c-linker-cys-NH 2)上进行了固相 N 端连接。作为两种并行方法,硫醇与马来酰亚胺和卤乙酰基的强亲和力被用于随后的基于氰基有机金属核 C2 和 C3 的后 SPPS 加成。将硫醇官能化的 PNA1(H-gly-a-g-t-c-t-g-c-linker-cys-NH 2)和 PNA2(C1-a-a-g-t-c-t-g-c-linker-cys-NH 2)分别与马来酰亚胺和氯乙酰衍生物 C2 和 C3 进行了类似迈克尔加成和硫醚连接。通过质谱(ESI-MS)和红外光谱对合成的钌(II)-氰基 PNA 低聚物进行了表征。1,924-2,074 cm (-1) 之间明显的 Mn-CO 红外振动谱段被用作标记,以确认 PNA 序列中存在环戊烯基单元,并使用 LC-MS 评估了 HPLC 纯化的 PNA 硫醚的纯度。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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