Kinetically Controlled Coassembly of Multichromophoric Peptide Hydrogelators and the Impacts on Energy Transport
Kinetically Controlled Coassembly of Multichromophoric Peptide Hydrogelators and the Impacts on Energy Transport
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DOI：
10.1021/jacs.7b04006
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发表时间：
2017-06-28
影响因子：
15
通讯作者：
Tovar, John D.
中科院分区：
文献类型：
--
作者：
Ardona, Herdeline Ann M.;Draper, Emily R.;Tovar, John D.
我们报道了一种基于多肽的多色性水凝胶体系，其中具有不同固有光谱能量的pi电子单元在多肽一维纳米结构中被空间控制，以在水环境中产生局域能量梯度。这是通过混合不同的pi-共轭多肽，然后通过溶液酸化启动自组装来实现的。我们可以通过选择组装触发器来改变组装的动力学和自分类的程度，从而改变酸化的动力学。葡萄糖-三角洲-内酯(GDL)的水解提供了缓慢的pH下降，允许基于细微的pK(A)差异逐步触发多肽成分进入基本上自分类的纳米结构，而HCl加成导致纳米结构中混合成分的快速形成。利用H-1核磁共振波谱和纤维X-射线衍射，我们确定了有利于自分类或亲密混合的条件和多肽混合物。溶液阶段的光物理研究提供了对组件内发生的能量传输过程与pi系统的结构组织的相关性的洞察。
We report a peptide-based multichromophoric hydrogelator system, wherein pi-electron units with different inherent spectral energies are spatially controlled within peptidic 1-D nanostructures to create localized energy gradients in aqueous environments. This is accomplished by mixing different pi-conjugated peptides prior to initiating self assembly through solution acidification. We can vary the kinetics of the assembly and the degree of self-sorting through the choice of the assembly trigger, which changes the kinetics of acidification. The hydrolysis of glucono-delta-lactone (GdL) provides a slow pH drop that allows for stepwise triggering of peptide components into essentially self-sorted nanostructures based on subtle pK(a) differences, whereas HCl addition leads to a rapid formation of mixed components within a nanostructure. Using H-1 NMR spectroscopy and fiber X-ray diffraction, we determine the conditions and peptide mixtures that favor self-sorting or intimate comixing. Photophysical investigations in the solution phase provide insight into the correlation of energy-transport processes occurring within the assemblies to the structural organization of the pi-systems.