Department of Materials Science and Engineering, University of California-Berkeley, Berkeley, California, USA.
J Am Chem Soc. 2012 Jul 18;134(28):11807-14. doi: 10.1021/ja3048128. Epub 2012 Jul 9.
Despite increasing demands to employ amphiphilic micelles as nanocarriers and nanoreactors, it remains a significant challenge to simultaneously reduce the particle size and enhance the particle stability. Complementary to covalent chemical bonding and attractive intermolecular interactions, entropic repulsion can be incorporated by rational design in the headgroup of an amphiphile to generate small micelles with enhanced stability. A new family of amphiphilic peptide-polymer conjugates is presented where the hydrophilic headgroup is composed of a 3-helix coiled coil with poly(ethylene glycol) attached to the exterior of the helix bundle. When micelles form, the PEG chains are confined in close proximity and are compressed to act as a spring to generate lateral pressure. The formation of 3-helix bundles determines the location and the directionalities of the force vector of each PEG elastic spring so as to slow down amphiphile desorption. Since each component of the amphiphile can be readily tailored, these micelles provide numerous opportunities to meet current demands for organic nanocarriers with tunable stability in life science and energy science. Furthermore, present studies open new avenues to use energy arising from entropic polymer chain deformation to self-assemble energetically stable, single nanoscopic objects, much like repulsion that stabilizes bulk assemblies of colloidal particles.
尽管人们越来越要求将两亲性胶束用作纳米载体和纳米反应器,但同时减小粒径并提高颗粒稳定性仍然是一个重大挑战。除了共价化学键合和吸引力的分子间相互作用之外,还可以通过在两亲分子的头基中进行合理设计,将熵斥力纳入其中,从而生成具有增强稳定性的小胶束。本文介绍了一类新型的两亲肽-聚合物缀合物,其中亲水的头基由带有聚乙二醇(PEG)的 3 螺旋卷曲组成。当形成胶束时,PEG 链被限制在紧密的位置并被压缩,起到弹簧的作用以产生侧向压力。3 螺旋束的形成决定了每个 PEG 弹性弹簧的力矢量的位置和方向,从而减缓两亲分子的解吸。由于两亲分子的每个组成部分都可以很容易地进行定制,因此这些胶束为满足生命科学和能源科学中具有可调稳定性的有机纳米载体的当前需求提供了许多机会。此外,目前的研究为利用熵聚合物链变形产生的能量来自组装能量稳定的单纳米尺度物体开辟了新途径,就像胶体颗粒的集体组装的稳定性源于斥力一样。