Ruíz-Olles Jorge, Smith David K
Department of Chemistry , University of York , Heslington , York , YO10 5DD , UK . Email:
Chem Sci. 2018 May 30;9(25):5541-5550. doi: 10.1039/c8sc01071d. eCollection 2018 Jul 7.
This paper explores macroscopic-scale diffusion of the molecular-scale building blocks of two-component self-assembled organogel nanofibres using a diffusion cell in which two different gels are in contact with one another. Both components of the 'solid-like' nanofibres (lysine peptide dendron acids and amines) can diffuse through these gels and across a gel-gel interface, although diffusion is significantly slower than that of a non-interactive additive in the 'liquid-like' phase of the gel. Amine diffusion was probed by bringing similar gels with different amines into contact. Dendron acid diffusion was tested by bringing similar gels with enantiomeric dendrons into contact. Surprisingly, dendron and amine diffusion rates were similar, even though the peptide dendron is more intimately hydrogen bonded in the self-assembled nanofibres. It is proposed that thermal disassembly of the acid-amine complex delivers both components into the liquid-like phase, allowing them to diffuse a decomplexation/recomplexation mechanism. This is a rare observation in which molecules assembled into solid-like gel nanofibres are mobile - in dynamic equilibrium with the liquid-like phase. Gel nanofibre diffusion and reorganisation are vital in understanding dynamic materials processes such as metastability, self-healing and adaptability.
本文利用一个扩散池,研究了双组分自组装有机凝胶纳米纤维的分子尺度构建单元在宏观尺度上的扩散,该扩散池中两种不同的凝胶相互接触。“类固态”纳米纤维的两种组分(赖氨酸肽树枝状酸和胺)都可以扩散通过这些凝胶并穿过凝胶 - 凝胶界面,尽管扩散速度明显慢于凝胶“类液态”相中无相互作用添加剂的扩散速度。通过使含有不同胺的相似凝胶接触来探测胺的扩散。通过使含有对映体树枝状分子的相似凝胶接触来测试树枝状酸的扩散。令人惊讶的是,尽管肽树枝状分子在自组装纳米纤维中通过氢键结合得更紧密,但树枝状分子和胺的扩散速率相似。有人提出,酸 - 胺复合物的热解离将两种组分都输送到类液态相中,使它们能够通过一种解络合/再络合机制进行扩散。这是一个罕见的观察结果,即组装成类固态凝胶纳米纤维的分子是可移动的——与类液态相处于动态平衡。凝胶纳米纤维的扩散和重组对于理解诸如亚稳性、自愈性和适应性等动态材料过程至关重要。