Spacers for Geometrically Well-Defined Water-Soluble Molecular Rulers and Their Application.
Spacers for Geometrically Well-Defined Water-Soluble Molecular Rulers and Their Application.
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几何形状明确的水溶性分子尺的间隔物及其应用
DOI：
10.1021/acs.joc.6b00125
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Hülsmann
中科院分区：
文献类型：
--
作者：
Hülsmann
描述了在多步合成的非常后期阶段具有可根据特定需要（例如水溶性）调节的侧链的单分散低聚（对亚苯基乙炔基）（oligopPEs）的合成和应用。可调节的侧链允许规避与在合成的早期阶段分离高度亲水性化合物相关的问题。此外，这些oligPPE可以作为适应性强的高级构建模块储存，用于快速组装定制的间隔物和标尺。快速生长合成提供了具有用正交基团三甲基甲硅烷基和1-羟基-1-甲基乙基（HOP）保护的炔末端和用三异丙基甲硅烷基保护的炔丙氧基侧链的寡聚PPE。三个保护基团允许两个末端和侧链的独立修饰。HOP基团不仅作为保护基团，而且作为极性标签用于简单的产物分离。我们展示了这些oligopPEs作为Gd-PyMTA-spacer-Gd-PyMTA型水溶性Gd统治者的间隔物的一个应用，其中Gd-Gd距离为2.1-10.9 nm。为此目的，末端炔单元用于骨架组装和配体PyMTA的连接，并且炔丙氧基侧链用于在间隔物组装后通过点击反应连接水溶性聚（乙二醇）链。
The synthesis and application of monodisperse oligo(para-phenyleneethynylene)s (oligoPPEs) with side chains that are adjustable to specific needs, such as water solubility, on a very late stage of the multistep synthesis are described. The adjustable side chains allow for circumventing problems associated with the isolation of highly hydrophilic compounds during early stages of a synthesis. Furthermore, these oligoPPEs can be stocked as adaptable advanced building blocks for rapid assembly of tailor-made spacers and rulers. A rapid growth synthesis provides oligoPPEs with alkyne termini protected with the orthogonal groups trimethylsilyl and 1-hydroxy-1-methylethyl (HOP) and with propargyloxy side chains protected with the triisopropylsilyl group. The three protecting groups allow independent modification of the two termini and the side chains. The HOP group not only acts as a protecting group but also as a polar tag for simple product isolation. We demonstrate one application of these oligoPPEs as spacers for the water-soluble Gd rulers of the type Gd-PyMTA–spacer–Gd-PyMTA with Gd–Gd distances of 2.1–10.9 nm. For this purpose, the terminal alkyne units were used for backbone assembly and attachment of the ligand PyMTA, and the porpargyloxy side chains were used to attach water solubilizing poly(ethylene glycol) chains through a click reaction after spacer assembly.
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来自自旋标记膜结合蛋白的结构信息
DOI：
--
发表时间：
2013
期刊：
影响因子：
--
作者：
J. Klare;H. Steinhoff
通讯作者：
H. Steinhoff
影响因子：
15
作者：
Kiesewetter, Matthew K.;Corzilius, Bjoern;Smith, Albert A.;Griffin, Robert G.;Swager, Timothy M.
通讯作者：
Swager, Timothy M.
影响因子：
2.2
作者：
Doll, Andrin;Qi, Mian;Jeschke, Gunnar
通讯作者：
Jeschke, Gunnar
影响因子：
16.6
作者：
Joseph, Benesh;Sikora, Arthur;Bordignon, Enrica;Jeschke, Gunnar;Cafiso, David S.;Prisner, Thomas F.
通讯作者：
Prisner, Thomas F.
生物聚合物的定点硝基氧自旋标记
影响因子：
8.2
作者：
Sandip A. Shelke;S. Sigurdsson
通讯作者：
S. Sigurdsson