Self-assembly of hard helices: a rich and unconventional polymorphism

被引:36
作者
Kolli, Hima Bindu [1 ]
Frezza, Elisa [2 ]
Cinacchi, Giorgio [3 ,4 ]
Ferrarini, Alberta [2 ]
Giacometti, Achille [1 ]
Hudson, Toby S. [5 ]
De Michele, Cristiano [6 ]
Sciortino, Francesco [6 ]
机构
[1] Univ Venice, Dipartimento Sci Mol & Nanosist, I-30123 Venice, Italy
[2] Univ Padua, Dipartimento Sci Chim, I-35131 Padua, Italy
[3] Univ Autonoma Madrid, Dep Fis Teor Mat Condensada, Madrid 28049, Spain
[4] Univ Autonoma Madrid, Inst Fis Mat Condensada, Madrid 28049, Spain
[5] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia
[6] Univ Roma La Sapienza, Dipartimento Fis, I-00185 Rome, Italy
关键词
INTERFACIAL-TENSION; LIQUID; DNA; POLYMERS; PHASES; SHAPE;
D O I
10.1039/c4sm01305k
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Hard helices can be regarded as a paradigmatic elementary model for a number of natural and synthetic soft matter systems, all featuring the helix as their basic structural unit, from natural polynucleotides and polypeptides to synthetic helical polymers, and from bacterial flagella to colloidal helices. Here we present an extensive investigation of the phase diagram of hard helices using a variety of methods. Isobaric Monte Carlo numerical simulations are used to trace the phase diagram; on going from the low-density isotropic to the high-density compact phases a rich polymorphism is observed, exhibiting a special chiral screw-like nematic phase and a number of chiral and/or polar smectic phases. We present full characterization of the latter, showing that they have unconventional features, ascribable to the helical shape of the constituent particles. Equal area construction is used to locate the isotropic-to-nematic phase transition, and the results are compared with those stemming from an Onsager-like theory. Density functional theory is also used to study the nematic-to-screw-nematic phase transition; within the simplifying assumption of perfectly parallel helices, we compare different levels of approximation, that is second- and third-virial expansions and a Parsons-Lee correction.
引用
收藏
页码:8171 / 8187
页数:17
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