Lachmayr Kätchen K, Wentz Charlotte M, Sita Lawrence R
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742, USA.
Angew Chem Int Ed Engl. 2020 Jan 20;59(4):1521-1526. doi: 10.1002/anie.201912648. Epub 2019 Dec 6.
"One-component" soft material Frank-Kasper (FK) phases are an intriguing structural form of matter that possess periodically ordered structures arising from the self-reconfiguration and close packing of an initial assembly of identical "deformable" spheres into two or more size- or shape-distinct sets of particles. Significant challenges that must still be addressed to advance the field of soft matter FK phases further, however, include their rare and unpredictable occurrence, uncertain mechanisms of solid-state assembly, and low thermodynamic stability. Here we show that a readily-accessible sugar-polyolefin conjugate quantitatively produces an exceptionally stable solid-state FK A15 phase through a rapid and irreversible thermotropic order-order transition, which contrary to other prevailing proposed mechanisms, does not require mass transfer between particles or large structural reorganization in the bulk to establish unit cell non-equivalency. Our results provide the basis for a realistic strategy for obtaining practical and scalable quantities of a diverse range of sugar-polyolefin FK A15 phases with unique intrinsic physical properties and chemical reactivities not previously seen in such systems.
“单组分”软物质弗兰克 - 卡斯帕（FK）相是一种引人入胜的物质结构形式，它具有周期性有序结构，这种结构源于相同“可变形”球体的初始组装体通过自我重构和紧密堆积形成两组或更多组尺寸或形状不同的粒子集合。然而，要进一步推动软物质FK相领域的发展，仍必须解决的重大挑战包括它们出现的频率低且不可预测、固态组装机制不确定以及热力学稳定性低。在此我们表明，一种易于获得的糖 - 聚烯烃共轭物通过快速且不可逆的热致有序 - 有序转变定量地产生了一种异常稳定的固态FK A15相，与其他普遍提出的机制相反，该转变不需要粒子间的质量传递或本体中的大规模结构重组来建立晶胞不等价性。我们的结果为获得实际且可扩展数量的多种糖 - 聚烯烃FK A15相提供了现实策略的基础，这些相具有此类系统中前所未见的独特固有物理性质和化学反应性。
