Hulliger Jürg
Department of Chemistry and Biochemistry, University of Berne, Freiestrasse 3, 3012 Berne, Switzerland.
Chemistry. 2002 Oct 18;8(20):4579-86.
Assembling polar building blocks into a solid material by a Markov-chain process of unidirectional growth principally results in a metastable state that shows effects of macroscopic polarity. Stochastic polarity formation can be described by probabilities for the attachment of building blocks to a surface. Because of the polar symmetry of the building blocks, there is a fundamental difference in the probabilities for attaching them "tip-first" or "back-first" to growth sites at a surface. A difference in the corresponding probabilities drives the evolution of a vectorial property through a gain in configurational entropy. Examples from the mechanical, the crystalline and the biological world demonstrate growth-induced macroscopic polarity. In crystals, growth upon centrosymmetric seeds can produce twinned crystals with a "sectorwise" pyroelectric effect. Polarity formation in connective tissues is explained by a Markov-chain mechanism, which drives the self-assembly of collagen fibril segments. An unified stochastic growth model brings up a general concept for the formation of materials with polar properties.
通过单向生长的马尔可夫链过程将极性构建块组装成固体材料,主要会产生一种亚稳态,该亚稳态表现出宏观极性效应。随机极性形成可以用构建块附着到表面的概率来描述。由于构建块的极性对称性,将它们“尖端先”或“背面先”附着到表面生长位点的概率存在根本差异。相应概率的差异通过构型熵的增加驱动矢量性质的演化。来自机械、晶体和生物世界的例子展示了生长诱导的宏观极性。在晶体中,在中心对称晶种上生长可产生具有“扇形”热电效应的孪晶。结缔组织中的极性形成由马尔可夫链机制解释,该机制驱动胶原纤维段的自组装。一个统一的随机生长模型提出了形成具有极性性质材料的一般概念。